Aryl sulfide comprising benzylamine, synthesis method and application thereof

ABSTRACT

The invention belongs to the technical field of pesticides and specifically relates to an aryl sulfide containing a benzylamine structure, a synthesis method therefor, and an application thereof. The aryl sulfide is denoted as compound I. Also provided is an agriculturally acceptable salt of the aryl sulfide. The compound represented by formula I shows excellent effects on various harmful organisms, especially spider mites represented by  Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus Kanzawai Kishida, Panonychus citri , etc., and can be used for controlling all kinds of harmful mites.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of International Patent Application No. PCT/CN2020/000198 with an international filing date of Aug. 31, 2020, designating the United States, now pending, and further claims foreign priority benefits to Chinese Patent Application No. 201910900234.4 filed Sep. 23, 2019, and to Chinese Patent Application No. 202010796915.3 filed Aug. 10, 2020. The contents of all of the aforementioned applications, including any intervening amendments thereto, are incorporated herein by reference. Inquiries from the public to applicants or assignees concerning this document or the related applications should be directed to: Matthias Scholl P.C., Attn.: Dr. Matthias Scholl Esq., 245 First Street, 18th Floor, Cambridge, Mass. 02142.

BACKGROUND

The disclosure relates to the field of pesticides, and more particularly to an aryl sulfide comprising benzylamine, a synthesis method and application thereof.

The compound with the following general formula has acaricidal activity:

where A is oxygen or sulfur, R₅ is a substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted amino, nitrogen heterocycle, etc.

The following general formula compound exhibits acaricidal activity:

where R4 represents hydrogen, formyl, C₁₋₆ alkyl, or the like; R₅ and R₆ are the same or different and at each occurrence represent hydrogen, halogen, C₁₋₆ alkyl, or the like; R₇, R₈, R₉, R₁₀, R₁₁ are the same or different and at each occurrence represents hydrogen, halogen, or the like; X is oxygen or sulfur.

The active compounds mentioned above have low activity in the control of harmful substances, especially mites. Particularly, in the low usage dose, the acaricidal activity thereof is unsatisfactory, and the control effect on the drug-resistant Tetranychus is poor.

SUMMARY

In view of the low acaricidal activity for mite control in the prior art, the disclosure provides an aryl sulfide comprising benzylamine and its synthesis method and application. The results showed that the aryl sulfide derivatives represented by the following general formula showed excellent effects on various pests, especially on Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, and the like.

The disclosure provides an aryl sulfide comprising benzylamine, being represented by formula I, or an agriculturally acceptable salt thereof:

where:

n is 0, 1 or 2;

X and Y at each occurrence represent hydrogen, fluorine, chlorine, bromine, iodine, a cyano group, a C₁₋₄ alkyl, a C₁₋₄ haloalkyl, a C₁₋₄ alkoxy or a C₁₋₄ haloalkoxy;

R₁, R₂, R₃, R₄, and R₅ at each occurrence represent hydrogen, fluorine, chlorine, bromine, iodine, a cyano group, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, sulphydryl, C₁₋₁₀ alkyl, C₁₋₁₀ haloalkyl, C₁₋₁₀ alkoxy, C₁₋₁₀ haloalkoxy, C₁₋₁₀ alkoxycarbonyl, C₁₋₁₀ haloalkoxycarbonyl, C₁₋₁₀ alkylsulfonyloxy, C₁₋₁₀ alkyl sulfonyl, C₁₋₁₀ alkylthiol, C₁₋₁₀ haloalkylthiol, C₂₋₁₀ ethoxycarbonyl, C₁₋₁₀ alkyl carbonyl, amino carbonyl, C₁₋₁₀ N-alkyl carbonyl, N, N-dimethylcarbonyl, N, N-dimethylthiocarbonyl, C₁₋₁₀ N-alkyl thiocarbonyl, 2-oxoprooxycarbonyl, or methoxymethoxycarbonyl; and

R₆ represents C₁₋₆ haloalkyl, C₂₋₆ alkynyl, C₂₋₆ alkenyl, C₁₋₆ alkyl, C₃₋₆ cycloalkyl, or C₃₋₆ epoxy alkyl.

In a class of this embodiment, in formula I,

n is 0 or 1;

X is fluorine, chlorine, or methyl;

Y is chlorine or methyl;

R₁ is hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, hydroxymethyl, a cyano group, trifluoromethyl, C₁₋₃ alkyl, C₁₋₄ alkoxycarbonyl, acetyl, propionyl, C₁₋₃ alkoxy, ethylthio, 2-fluoroethanothioxy, 2-chloroethanothioxy, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, propylthio, 2,2,2-trifluoroethylsulfinyl, vinyloxycarbonyl, 2,2, 2-trifluoroethoxycarbonyl, or N-methylcarbonyl;

R₂ is hydrogen, fluorine, or chlorine;

R₃ is hydrogen, fluorine, chlorine, bromine, or a cyano group;

R₄ and R₅ at each occurrence represent hydrogen; and

R₆ is N-propyl or 2,2,2-trifluoroethyl.

In a class of this embodiment, in formula I,

n is 0 or 1;

X is fluorine;

Y is chlorine or methyl;

R₁ is methoxycarbonyl, ethoxycarbonyl, ethylthio, or 2,2,2-trifluoroethylthio;

R₂, R₄, and R₅ at each occurrence represent hydrogen;

R₃ is hydrogen, fluorine, chlorine, or a cyano group; and

R₆ is 2,2,2-trifluoroethyl.

In a class of this embodiment, the formula I comprises:

Representative compounds of the general formula I of the disclosure are shown in Table 1. However, the compounds of the disclosure are not limited to those listed therein. In addition, the serial numbers of corresponding compounds are also listed in Table 1.

According to the type of substituents, the compounds of the aryl sulfide derivatives and aryl sulfur oxide derivatives of the disclosure present in the form of E-type and Z-type geometric isomers, and the compounds of the disclosure comprise the E-type, Z-type or a mixture thereof in an arbitrary proportion.

The following abbreviations in Table 1 denote the following groups respectively:

Me: methyl;

Et: ethyl;

tBu: tert butyl;

CF₃: trifluoromethyl;

AC: acetyl group;

nPropyl: n-propyl;

isopropyl: Isopropyl;

nButyl: n-butyl;

nPentyl: n-amyl;

nHexyl: n-hexyl;

nHeptyl: n-heptyl;

nOctyl: n-octyl;

nNonyl: nonyl;

nDecyl: n-decyl.

TABLE 1 List of compounds I

No. X Y n R₁ R₂ R₃ R₄ R₅ R₆ 1 F Me 0 Me H H H H CH₂CF₃ 2 F Me 1 Me H H H H CH₂CF₃ 3 F Me 0 CF₃ H H H H CH₂CF₃ 4 F Me 1 CF₃ H H H H CH₂CF₃ 5 F Me 0 Et H H H H CH₂CF₃ 6 F Me 1 Et H H H H CH₂CF₃ 7 F Me 0 nPropyl H H H H CH₂CF₃ 8 F Me 1 nPropyl H H H H CH₂CF₃ 9 F Me 0 isopropyl H H H H CH₂CF₃ 10 F Me 1 isopropyl H H H H CH₂CF₃ 11 F Me 0 nButyl H H H H CH₂CF₃ 12 F Me 1 nButyl H H H H CH₂CF₃ 13 F Me 0 nPentyl H H H H CH₂CF₃ 14 F Me 1 nPentyl H H H H CH₂CF₃ 15 F Me 0 nHexyl H H H H CH₂CF₃ 16 F Me 1 nHexyl H H H H CH₂CF₃ 17 F Me 0 nHeptyl H H H H CH₂CF₃ 18 F Me 1 nHeptyl H H H H CH₂CF₃ 19 F Me 0 nOctyl H H H H CH₂CF₃ 20 F Me 1 nOctyl H H H H CH₂CF₃ 21 F Me 0 nNonyl H H H H CH₂CF₃ 22 F Me 1 nNonyl H H H H CH₂CF₃ 23 F Me 0 nDecyl H H H H CH₂CF₃ 24 F Me 1 nDecyl H H H H CH₂CF₃ 25 F Me 0 F H H H H CH₂CF₃ 26 F Me 1 F H H H H CH₂CF₃ 27 F Me 0 Cl H H H H CH₂CF₃ 28 F Me 1 Cl H H H H CH₂CF₃ 29 F Me 0 Br H H H H CH₂CF₃ 30 F Me 1 Br H H H H CH₂CF₃ 31 F Me 0 I H H H H CH₂CF₃ 32 F Me 1 I H H H H CH₂CF₃ 33 F Me 0 CN H H H H CH₂CF₃ 34 F Me 1 CN H H H H CH₂CF₃ 35 F Me 0 NO₂ H H H H CH₂CF₃ 36 F Me 1 NO₂ H H H H CH₂CF₃ 37 F Me 0 NH₂ H H H H CH₂CF₃ 38 F Me 1 NH₂ H H H H CH₂CF₃ 39 F Me 0 CH₂OH H H H H CH₂CF₃ 40 F Me 1 CH₂OH H H H H CH₂CF₃ 41 F Me 0 COCH₃ H H H H CH₂CF₃ 42 F Me 1 COCH₃ H H H H CH₂CF₃ 43 F Me 0 COCH₂CH₃ H H H H CH₂CF₃ 44 F Me 1 COCH₂CH₃ H H H H CH₂CF₃ 45 F Me 0 COCH₂CH₂CH₃ H H H H CH₂CF₃ 46 F Me 1 COCH₂CH₂CH₃ H H H H CH₂CF₃ 47 F Me 0 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 48 F Me 1 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 49 F Me 0 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 50 F Me 1 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 51 F Me 0 COOH H H H H CH₂CF₃ 52 F Me 1 COOH H H H H CH₂CF₃ 53 F Me 0 CO₂CH₃ H H H H CH₂CF₃ 54 F Me 1 CO₂CH₃ H H H H CH₂CF₃ 55 F Me 0 CO₂CH₂CH₃ H H H H CH₂CF₃ 56 F Me 1 CO₂CH₂CH₃ H H H H CH₂CF₃ 57 F Me 0 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 58 F Me 1 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 59 F Me 0 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 60 F Me 1 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 61 F Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 62 F Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 63 F Me 0 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 64 F Me 1 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 65 F Me 0 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 66 F Me 1 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 67 F Me 0 CO₂CH═CH₂ H H H H CH₂CF₃ 68 F Me 1 CO₂CH═CH₂ H H H H CH₂CF₃ 69 F Me 0 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 70 F Me 1 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 71 F Me 0 CO₂CH₂CF₃ H H H H CH₂CF₃ 72 F Me 1 CO₂CH₂CF₃ H H H H CH₂CF₃ 73 F Me 0 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 74 F Me 1 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 75 F Me 0 CO₂CH₂CH₂Br H H H H CH₂CF₃ 76 F Me 1 CO₂CH₂CH₂Br H H H H CH₂CF₃ 77 F Me 0 CO₂CH₂OCH₃ H H H H CH₂CF₃ 78 F Me 1 CO₂CH₂COCH₃ H H H H CH₂CF₃ 79 F Me 0 CONH₂ H H H H CH₂CF₃ 80 F Me 1 CONH₂ H H H H CH₂CF₃ 81 F Me 0 CONHCH₃ H H H H CH₂CF₃ 82 F Me 1 CONHCH₃ H H H H CH₂CF₃ 83 F Me 0 CON(CH₃)₂ H H H H CH₂CF₃ 84 F Me 1 CON(CH₃)₂ H H H H CH₂CF₃ 85 F Me 0 CONHCH₂CH₃ H H H H CH₂CF₃ 86 F Me 1 CONHCH₂CH₃ H H H H CH₂CF₃ 87 F Me 0 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 88 F Me 1 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 89 F Me 0 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 90 F Me 1 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 91 F Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 92 F Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 93 F Me 0 OH H H H H CH₂CF₃ 94 F Me 1 OH H H H H CH₂CF₃ 95 F Me 0 OCH₃ H H H H CH₂CF₃ 96 F Me 1 OCH₃ H H H H CH₂CF₃ 97 F Me 0 OCH₂CH₃ H H H H CH₂CF₃ 98 F Me 1 OCH₂CH₃ H H H H CH₂CF₃ 99 F Me 0 OCH₂CH₂CH₃ H H H H CH₂CF₃ 100 F Me 1 OCH₂CH₂CH₃ H H H H CH₂CF₃ 101 F Me 0 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 102 F Me 1 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 103 F Me 0 OCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 104 F Me 1 SH H H H H CH₂CF₃ 105 F Me 0 SH H H H H CH₂CF₃ 106 F Me 1 SCH₃ H H H H CH₂CF₃ 107 F Me 0 SCH₃ H H H H CH₂CF₃ 108 F Me 1 SCH₂CH₃ H H H H CH₂CF₃ 109 F Me 0 SCH₂CH₃ H H H H CH₂CF₃ 110 F Me 1 SCH₂CH₂CH₃ H H H H CH₂CF₃ 111 F Me 0 SCH₂CH₂CH₃ H H H H CH₂CF₃ 112 F Me 1 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 113 F Me 0 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 114 F Me 1 SCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 115 Me Me 0 Me H H H H CH₂CF₃ 116 Me Me 1 Me H H H H CH₂CF₃ 117 Me Me 0 CF₃ H H H H CH₂CF₃ 118 Me Me 1 CF₃ H H H H CH₂CF₃ 119 Me Me 0 Et H H H H CH₂CF₃ 120 Me Me 1 Et H H H H CH₂CF₃ 121 Me Me 0 nPropyl H H H H CH₂CF₃ 122 Me Me 1 nPropyl H H H H CH₂CF₃ 123 Me Me 0 isopropyl H H H H CH₂CF₃ 124 Me Me 1 isopropyl H H H H CH₂CF₃ 125 Me Me 0 nButyl H H H H CH₂CF₃ 126 Me Me 1 nButyl H H H H CH₂CF₃ 127 Me Me 0 nPentyl H H H H CH₂CF₃ 128 Me Me 1 nPentyl H H H H CH₂CF₃ 129 Me Me 0 nHexyl H H H H CH₂CF₃ 130 Me Me 1 nHexyl H H H H CH₂CF₃ 131 Me Me 0 nHeptyl H H H H CH₂CF₃ 132 Me Me 1 nHeptyl H H H H CH₂CF₃ 133 Me Me 0 nOctyl H H H H CH₂CF₃ 134 Me Me 1 nOctyl H H H H CH₂CF₃ 135 Me Me 0 nNonyl H H H H CH₂CF₃ 136 Me Me 1 nNonyl H H H H CH₂CF₃ 137 Me Me 0 nDecyl H H H H CH₂CF₃ 138 Me Me 1 nDecyl H H H H CH₂CF₃ 139 Me Me 0 F H H H H CH₂CF₃ 140 Me Me 1 F H H H H CH₂CF₃ 141 Me Me 0 Cl H H H H CH₂CF₃ 142 Me Me 1 Cl H H H H CH₂CF₃ 143 Me Me 0 Br H H H H CH₂CF₃ 144 Me Me 1 Br H H H H CH₂CF₃ 145 Me Me 0 I H H H H CH₂CF₃ 146 Me Me 1 I H H H H CH₂CF₃ 147 Me Me 0 CN H H H H CH₂CF₃ 148 Me Me 1 CN H H H H CH₂CF₃ 149 Me Me 0 NO₂ H H H H CH₂CF₃ 150 Me Me 1 NO₂ H H H H CH₂CF₃ 151 Me Me 0 NH₂ H H H H CH₂CF₃ 152 Me Me 1 NH₂ H H H H CH₂CF₃ 153 Me Me 0 CH₂OH H H H H CH₂CF₃ 154 Me Me 1 CH₂OH H H H H CH₂CF₃ 155 Me Me 0 COCH₃ H H H H CH₂CF₃ 156 Me Me 1 COCH₃ H H H H CH₂CF₃ 157 Me Me 0 COCH₂CH₃ H H H H CH₂CF₃ 158 Me Me 1 COCH₂CH₃ H H H H CH₂CF₃ 159 Me Me 0 COCH₂CH₂CH₃ H H H H CH₂CF₃ 160 Me Me 1 COCH₂CH₂CH₃ H H H H CH₂CF₃ 161 Me Me 0 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 162 Me Me 1 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 163 Me Me 0 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 164 Me Me 1 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 165 Me Me 0 COOH H H H H CH₂CF₃ 166 Me Me 1 COOH H H H H CH₂CF₃ 167 Me Me 0 CO₂CH₃ H H H H CH₂CF₃ 168 Me Me 1 CO₂CH₃ H H H H CH₂CF₃ 169 Me Me 0 CO₂CH₂CH₃ H H H H CH₂CF₃ 170 Me Me 1 CO₂CH₂CH₃ H H H H CH₂CF₃ 171 Me Me 0 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 172 Me Me 1 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 173 Me Me 0 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 174 Me Me 1 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 175 Me Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 176 Me Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 177 Me Me 0 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 178 Me Me 1 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 179 Me Me 0 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 180 Me Me 1 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 181 Me Me 0 CO₂CH═CH₂ H H H H CH₂CF₃ 182 Me Me 1 CO₂CH═CH₂ H H H H CH₂CF₃ 183 Me Me 0 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 184 Me Me 1 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 185 Me Me 0 CO₂CH₂CF₃ H H H H CH₂CF₃ 186 Me Me 1 CO₂CH₂CF₃ H H H H CH₂CF₃ 187 Me Me 0 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 188 Me Me 1 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 189 Me Me 0 CO₂CH₂CH₂Br H H H H CH₂CF₃ 190 Me Me 1 CO₂CH₂CH₂Br H H H H CH₂CF₃ 191 Me Me 0 CO₂CH₂OCH₃ H H H H CH₂CF₃ 192 Me Me 1 CO₂CH₂COCH₃ H H H H CH₂CF₃ 193 Me Me 0 CONH₂ H H H H CH₂CF₃ 194 Me Me 1 CONH₂ H H H H CH₂CF₃ 195 Me Me 0 CONHCH₃ H H H H CH₂CF₃ 196 Me Me 1 CONHCH₃ H H H H CH₂CF₃ 197 Me Me 0 CON(CH₃)₂ H H H H CH₂CF₃ 198 Me Me 1 CON(CH₃)₂ H H H H CH₂CF₃ 199 Me Me 0 CONHCH₂CH₃ H H H H CH₂CF₃ 200 Me Me 1 CONHCH₂CH₃ H H H H CH₂CF₃ 201 Me Me 0 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 202 Me Me 1 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 203 Me Me 0 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 204 Me Me 1 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 205 Me Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 206 Me Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 207 Me Me 0 OH H H H H CH₂CF₃ 208 Me Me 1 OH H H H H CH₂CF₃ 209 Me Me 0 OCH₃ H H H H CH₂CF₃ 210 Me Me 1 OCH₃ H H H H CH₂CF₃ 211 Me Me 0 OCH₂CH₃ H H H H CH₂CF₃ 212 Me Me 1 OCH₂CH₃ H H H H CH₂CF₃ 213 Me Me 0 OCH₂CH₂CH₃ H H H H CH₂CF₃ 214 Me Me 1 OCH₂CH₂CH₃ H H H H CH₂CF₃ 215 Me Me 0 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 216 Me Me 1 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 217 Me Me 0 OCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 218 Me Me 1 SH H H H H CH₂CF₃ 219 Me Me 0 SH H H H H CH₂CF₃ 220 Me Me 1 SCH₃ H H H H CH₂CF₃ 221 Me Me 0 SCH₃ H H H H CH₂CF₃ 222 Me Me 1 SCH₂CH₃ H H H H CH₂CF₃ 223 Me Me 0 SCH₂CH₃ H H H H CH₂CF₃ 224 Me Me 1 SCH₂CH₂CH₃ H H H H CH₂CF₃ 225 Me Me 0 SCH₂CH₂CH₃ H H H H CH₂CF₃ 226 Me Me 1 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 227 Me Me 0 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 228 Me Me 1 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 229 F Me 0 H F H H H CH₂CF₃ 230 F Me 1 H F H H H CH₂CF₃ 231 F Me 0 H Cl H H H CH₂CF₃ 232 F Me 1 H Cl H H H CH₂CF₃ 233 F Me 0 H Br H H H CH₂CF₃ 234 F Me 1 H Br H H H CH₂CF₃ 235 F Me 0 H I H H H CH₂CF₃ 236 F Me 1 H I H H H CH₂CF₃ 237 F Me 0 H Me H H H CH₂CF₃ 238 F Me 1 H Me H H H CH₂CF₃ 239 F Me 0 H OCH₃ H H H CH₂CF₃ 240 F Me 1 H OCH₃ H H H CH₂CF₃ 241 F Me 0 H NO₂ H H H CH₂CF₃ 242 F Me 1 H NO₂ H H H CH₂CF₃ 243 F Me 0 H CN H H H CH₂CF₃ 244 F Me 1 H CN H H H CH₂CF₃ 245 F Me 0 H CO₂CH₃ H H H CH₂CF₃ 246 F Me 1 H CO₂CH₃ H H H CH₂CF₃ 247 F Me 0 H Cl Cl H H CH₂CF₃ 248 F Me 1 H Cl Cl H H CH₂CF₃ 249 F Me 0 H F CL H H CH₂CF₃ 250 F Me 1 H F Cl H H CH₂CF₃ 251 F Me 0 H Br H F H CH₂CF₃ 252 F Me 1 H Br H F H CH₂CF₃ 253 F Me 0 Me H F H H CH₂CF₃ 254 F Me 1 Me H F H H CH₂CF₃ 255 F Me 0 Et H F H H CH₂CF₃ 256 F Me 1 Et H F H H CH₂CF₃ 257 F Me 0 nPropyl H F H H CH₂CF₃ 258 F Me 1 nPropyl H F H H CH₂CF₃ 259 F Me 0 isopropyl H F H H CH₂CF₃ 260 F Me 1 isopropyl H F H H CH₂CF₃ 261 F Me 0 nButyl H F H H CH₂CF₃ 262 F Me 1 nButyl H F H H CH₂CF₃ 263 F Me 0 nPentyl H F H H CH₂CF₃ 264 F Me 1 nPentyl H F H H CH₂CF₃ 265 F Me 0 nHexyl H F H H CH₂CF₃ 266 F Me 1 nHexyl H F H H CH₂CF₃ 267 F Me 0 nHeptyl H F H H CH₂CF₃ 268 F Me 1 nHeptyl H F H H CH₂CF₃ 269 F Me 0 nOctyl H F H H CH₂CF₃ 270 F Me 1 nOctyl H F H H CH₂CF₃ 271 F Me 0 nNonyl H F H H CH₂CF₃ 272 F Me 1 nNonyl H F H H CH₂CF₃ 273 F Me 0 nDecyl H F H H CH₂CF₃ 274 F Me 1 nDecyl H F H H CH₂CF₃ 275 F Me 0 F H F H H CH₂CF₃ 276 F Me 1 F H F H H CH₂CF₃ 277 F Me 0 Cl H F H H CH₂CF₃ 278 F Me 1 Cl H F H H CH₂CF₃ 279 F Me 0 Br H F H H CH₂CF₃ 280 F Me 1 Br H F H H CH₂CF₃ 281 F Me 0 I H F H H CH₂CF₃ 282 F Me 1 I H F H H CH₂CF₃ 283 F Me 0 CN H F H H CH₂CF₃ 284 F Me 1 CN H F H H CH₂CF₃ 285 F Me 0 NO₂ H F H H CH₂CF₃ 286 F Me 1 NO₂ H F H H CH₂CF₃ 287 F Me 0 NH₂ H F H H CH₂CF₃ 288 F Me 1 NH₂ H F H H CH₂CF₃ 289 F Me 0 CH₂OH H F H H CH₂CF₃ 290 F Me 1 CH₂OH H F H H CH₂CF₃ 291 F Me 0 COCH₃ H F H H CH₂CF₃ 292 F Me 1 COCH₃ H F H H CH₂CF₃ 293 F Me 0 COCH₂CH₃ H F H H CH₂CF₃ 294 F Me 1 COCH₂CH₃ H F H H CH₂CF₃ 295 F Me 0 COCH₂CH₂CH₃ H F H H CH₂CF₃ 296 F Me 1 COCH₂CH₂CH₃ H F H H CH₂CF₃ 297 F Me 0 COCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 298 F Me 1 COCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 299 F Me 0 COCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 300 F Me 1 COCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 301 F Me 0 COOH H F H H CH₂CF₃ 302 F Me 1 COOH H F H H CH₂CF₃ 303 F Me 0 CO₂CH₃ H F H H CH₂CF₃ 304 F Me 1 CO₂CH₃ H F H H CH₂CF₃ 305 F Me 0 CO₂CH₂CH₃ H F H H CH₂CF₃ 306 F Me 1 CO₂CH₂CH₃ H F H H CH₂CF₃ 307 F Me 0 CO₂CH₂CH₂CH₃ H F H H CH₂CF₃ 308 F Me 1 CO₂CH₂CH₂CH₃ H F H H CH₂CF₃ 309 F Me 0 CO₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 310 F Me 1 CO₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 311 F Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 312 F Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 313 F Me 0 CO₂CH(CH₃)₂ H F H H CH₂CF₃ 314 F Me 1 CO₂CH(CH₃)₂ H F H H CH₂CF₃ 315 F Me 0 CO₂CH₂CH(CH₃)₂ H F H H CH₂CF₃ 316 F Me 1 CO₂CH₂CH(CH₃)₂ H F H H CH₂CF₃ 317 F Me 0 CO₂CH═CH₂ H F H H CH₂CF₃ 318 F Me 1 CO₂CH═CH₂ H F H H CH₂CF₃ 319 F Me 0 CO₂CH₂CH═CH₂ H F H H CH₂CF₃ 320 F Me 1 CO₂CH₂CH═CH₂ H F H H CH₂CF₃ 321 F Me 0 CO₂CH₂CF₃ H F H H CH₂CF₃ 322 F Me 1 CO₂CH₂CF₃ H F H H CH₂CF₃ 323 F Me 0 CO₂CH₂CH₂Cl H F H H CH₂CF₃ 324 F Me 1 CO₂CH₂CH₂Cl H F H H CH₂CF₃ 325 F Me 0 CO₂CH₂CH₂Br H F H H CH₂CF₃ 326 F Me 1 CO₂CH₂CH₂Br H F H H CH₂CF₃ 327 F Me 0 CO₂CH₂OCH₃ H F H H CH₂CF₃ 328 F Me 1 CO₂CH₂COCH₃ H F H H CH₂CF₃ 329 F Me 0 CONH₂ H F H H CH₂CF₃ 330 F Me 1 CONH₂ H F H H CH₂CF₃ 331 F Me 0 CONHCH₃ H F H H CH₂CF₃ 332 F Me 1 CONHCH₃ H F H H CH₂CF₃ 333 F Me 0 CON(CH₃)₂ H F H H CH₂CF₃ 334 F Me 1 CON(CH₃)₂ H F H H CH₂CF₃ 335 F Me 0 CONHCH₂CH₃ H F H H CH₂CF₃ 336 F Me 1 CONHCH₂CH₃ H F H H CH₂CF₃ 337 F Me 0 CONHCH₂CH₂CH₃ H F H H CH₂CF₃ 338 F Me 1 CONHCH₂CH₂CH₃ H F H H CH₂CF₃ 339 F Me 0 CONHCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 340 F Me 1 CONHCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 341 F Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 342 F Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H F H H CH2CF3 343 F Me 0 CSNHCH₃ H F H H CH2CF3 344 F Me 1 CSNHCH₃ H F H H CH2CF3 345 F Me 0 CSN(CH₃)₂ H F H H CH2CF3 346 F Me 1 CSN(CH₃)₂ H F H H CH2CF3 347 F Me 0 CSNHCH₂CH₃ H F H H CH2CF3 348 F Me 1 CSNHCH₂CH₃ H F H H CH2CF3 349 F Me 0 CONHCH₂CH₂CH₃ H F H H CH2CF3 350 F Me 1 CONHCH₂CH₂CH₃ H F H H CH2CF3 351 F Me 0 OH H F H H CH₂CF₃ 352 F Me 1 OH H F H H CH₂CF₃ 353 F Me 0 OCH₃ H F H H CH₂CF₃ 354 F Me 1 OCH₃ H F H H CH₂CF₃ 355 F Me 0 OCH₂CH₃ H F H H CH₂CF₃ 356 F Me 1 OCH₂CH₃ H F H H CH₂CF₃ 357 F Me 0 OCH₂CH₂CH₃ H F H H CH₂CF₃ 358 F Me 1 OCH₂CH₂CH₃ H F H H CH₂CF₃ 359 F Me 0 OCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 360 F Me 1 OCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 361 F Me 0 OCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 362 F Me 1 SH H F H H CH₂CF₃ 363 F Me 0 SH H F H H CH₂CF₃ 364 F Me 1 SCH₃ H F H H CH₂CF₃ 365 F Me 0 SCH₃ H F H H CH₂CF₃ 366 F Me 1 SCH₂CH₃ H F H H CH₂CF₃ 367 F Me 0 SCH₂CH₃ H F H H CH₂CF₃ 368 F Me 1 SCH₂CH₂CH₃ H F H H CH₂CF₃ 369 F Me 0 SCH₂CH₂CH₃ H F H H CH₂CF₃ 370 F Me 1 SCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 371 F Me 0 SCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 372 F Me 1 SCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 373 Me Me 0 Me H F H H CH₂CF₃ 374 Me Me 1 Me H F H H CH₂CF₃ 375 Me Me 0 Et H F H H CH₂CF₃ 376 Me Me 1 Et H F H H CH₂CF₃ 377 Me Me 0 nPropyl H F H H CH₂CF₃ 378 Me Me 1 nPropyl H F H H CH₂CF₃ 379 Me Me 0 isopropyl H F H H CH₂CF₃ 380 Me Me 1 isopropyl H F H H CH₂CF₃ 381 Me Me 0 nButyl H F H H CH₂CF₃ 382 Me Me 1 nButyl H F H H CH₂CF₃ 383 Me Me 0 nPentyl H F H H CH₂CF₃ 384 Me Me 1 nPentyl H F H H CH₂CF₃ 385 Me Me 0 nHexyl H F H H CH₂CF₃ 386 Me Me 1 nHexyl H F H H CH₂CF₃ 387 Me Me 0 nHeptyl H F H H CH₂CF₃ 388 Me Me 1 nHeptyl H F H H CH₂CF₃ 389 Me Me 0 nOctyl H F H H CH₂CF₃ 390 Me Me 1 nOctyl H F H H CH₂CF₃ 391 Me Me 0 nNonyl H F H H CH₂CF₃ 392 Me Me 1 nNonyl H F H H CH₂CF₃ 393 Me Me 0 nDecyl H F H H CH₂CF₃ 394 Me Me 1 nDecyl H F H H CH₂CF₃ 395 Me Me 0 F H F H H CH₂CF₃ 396 Me Me 1 F H F H H CH₂CF₃ 397 Me Me 0 Cl H F H H CH₂CF₃ 398 Me Me 1 Cl H F H H CH₂CF₃ 399 Me Me 0 Br H F H H CH₂CF₃ 400 Me Me 1 Br H F H H CH₂CF₃ 401 Me Me 0 I H F H H CH₂CF₃ 402 Me Me 1 I H F H H CH₂CF₃ 403 Me Me 0 CN H F H H CH₂CF₃ 404 Me Me 1 CN H F H H CH₂CF₃ 405 Me Me 0 NO₂ H F H H CH₂CF₃ 406 Me Me 1 NO₂ H F H H CH₂CF₃ 407 Me Me 0 NH₂ H F H H CH₂CF₃ 408 Me Me 1 NH₂ H F H H CH₂CF₃ 409 Me Me 0 CH₂OH H F H H CH₂CF₃ 410 Me Me 1 CH₂OH H F H H CH₂CF₃ 411 Me Me 0 COCH₃ H F H H CH₂CF₃ 412 Me Me 1 COCH₃ H F H H CH₂CF₃ 413 Me Me 0 COCH₂CH₃ H F H H CH₂CF₃ 414 Me Me 1 COCH₂CH₃ H F H H CH₂CF₃ 415 Me Me 0 COCH₂CH₂CH₃ H F H H CH₂CF₃ 416 Me Me 1 COCH₂CH₂CH₃ H F H H CH₂CF₃ 417 Me Me 0 COCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 418 Me Me 1 COCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 419 Me Me 0 COCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 420 Me Me 1 COCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 421 Me Me 0 COOH H F H H CH₂CF₃ 422 Me Me 1 COOH H F H H CH₂CF₃ 423 Me Me 0 CO₂CH₃ H F H H CH₂CF₃ 424 Me Me 1 CO₂CH₃ H F H H CH₂CF₃ 425 Me Me 0 CO₂CH₂CH₃ H F H H CH₂CF₃ 426 Me Me 1 CO₂CH₂CH₃ H F H H CH₂CF₃ 427 Me Me 0 CO₂CH₂CH₂CH₃ H F H H CH₂CF₃ 428 Me Me 1 CO₂CH₂CH₂CH₃ H F H H CH₂CF₃ 429 Me Me 0 CO₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 430 Me Me 1 CO₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 431 Me Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 432 Me Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 433 Me Me 0 CO₂CH(CH₃)₂ H F H H CH₂CF₃ 434 Me Me 1 CO₂CH(CH₃)₂ H F H H CH₂CF₃ 435 Me Me 0 CO₂CH₂CH(CH₃)₂ H F H H CH₂CF₃ 436 Me Me 1 CO₂CH₂CH(CH₃)₂ H F H H CH₂CF₃ 437 Me Me 0 CO₂CH═CH₂ H F H H CH₂CF₃ 438 Me Me 1 CO₂CH═CH₂ H F H H CH₂CF₃ 439 Me Me 0 CO₂CH₂CH═CH₂ H F H H CH₂CF₃ 440 Me Me 1 CO₂CH₂CH═CH₂ H F H H CH₂CF₃ 441 Me Me 0 CO₂CH₂CF₃ H F H H CH₂CF₃ 442 Me Me 1 CO₂CH₂CF₃ H F H H CH₂CF₃ 443 Me Me 0 CO₂CH₂CH₂Cl H F H H CH₂CF₃ 444 Me Me 1 CO₂CH₂CH₂Cl H F H H CH₂CF₃ 445 Me Me 0 CO₂CH₂CH₂Br H F H H CH₂CF₃ 446 Me Me 1 CO₂CH₂CH₂Br H F H H CH₂CF₃ 447 Me Me 0 CO₂CH₂OCH₃ H F H H CH₂CF₃ 448 Me Me 1 CO₂CH₂COCH₃ H F H H CH₂CF₃ 449 Me Me 0 CONH₂ H F H H CH₂CF₃ 450 Me Me 1 CONH₂ H F H H CH₂CF₃ 451 Me Me 0 CONHCH₃ H F H H CH₂CF₃ 452 Me Me 1 CONHCH₃ H F H H CH₂CF₃ 453 Me Me 0 CON(CH₃)₂ H F H H CH₂CF₃ 454 Me Me 1 CON(CH₃)₂ H F H H CH₂CF₃ 455 Me Me 0 CONHCH₂CH₃ H F H H CH₂CF₃ 456 Me Me 1 CONHCH₂CH₃ H F H H CH₂CF₃ 457 Me Me 0 CONHCH₂CH₂CH₃ H F H H CH₂CF₃ 458 Me Me 1 CONHCH₂CH₂CH₃ H F H H CH₂CF₃ 459 Me Me 0 CONHCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 460 Me Me 1 CONHCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 461 Me Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 462 Me Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 463 Me Me 0 OH H F H H CH₂CF₃ 464 Me Me 1 OH H F H H CH₂CF₃ 465 Me Me 0 OCH₃ H F H H CH₂CF₃ 466 Me Me 1 OCH₃ H F H H CH₂CF₃ 467 Me Me 0 OCH₂CH₃ H F H H CH₂CF₃ 468 Me Me 1 OCH₂CH₃ H F H H CH₂CF₃ 469 Me Me 0 OCH₂CH₂CH₃ H F H H CH₂CF₃ 470 Me Me 1 OCH₂CH₂CH₃ H F H H CH₂CF₃ 471 Me Me 0 OCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 472 Me Me 1 OCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 473 Me Me 0 OCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 474 Me Me 1 SH H F H H CH₂CF₃ 475 Me Me 0 SH H F H H CH₂CF₃ 476 Me Me 1 SCH₃ H F H H CH₂CF₃ 477 Me Me 0 SCH₃ H F H H CH₂CF₃ 478 Me Me 1 SCH₂CH₃ H F H H CH₂CF₃ 479 Me Me 0 SCH₂CH₃ H F H H CH₂CF₃ 480 Me Me 1 SCH₂CH₂CH₃ H F H H CH₂CF₃ 481 Me Me 0 SCH₂CH₂CH₃ H F H H CH₂CF₃ 482 Me Me 1 SCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 483 Me Me 0 SCH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 484 Me Me 1 SCH₂CH₂CH₂CH₂CH₃ H F H H CH₂CF₃ 485 F Me 0 Me H Cl H H CH₂CF₃ 486 F Me 1 Me H Cl H H CH₂CF₃ 487 F Me 0 Et H Cl H H CH₂CF₃ 488 F Me 1 Et H Cl H H CH₂CF₃ 489 F Me 0 nPropyl H Cl H H CH₂CF₃ 490 F Me 1 nPropyl H Cl H H CH₂CF₃ 491 F Me 0 isopropyl H Cl H H CH₂CF₃ 492 F Me 1 isopropyl H Cl H H CH₂CF₃ 493 F Me 0 nButyl H Cl H H CH₂CF₃ 494 F Me 1 nButyl H Cl H H CH₂CF₃ 495 F Me 0 nPentyl H Cl H H CH₂CF₃ 496 F Me 1 nPentyl H Cl H H CH₂CF₃ 497 F Me 0 nHexyl H Cl H H CH₂CF₃ 498 F Me 1 nHexyl H Cl H H CH₂CF₃ 499 F Me 0 nHeptyl H Cl H H CH₂CF₃ 500 F Me 1 nHeptyl H Cl H H CH₂CF₃ 501 F Me 0 nOctyl H Cl H H CH₂CF₃ 502 F Me 1 nOctyl H Cl H H CH₂CF₃ 503 F Me 0 nNonyl H Cl H H CH₂CF₃ 504 F Me 1 nNonyl H Cl H H CH₂CF₃ 505 F Me 0 nDecyl H Cl H H CH₂CF₃ 506 F Me 1 nDecyl H Cl H H CH₂CF₃ 507 F Me 0 F H Cl H H CH₂CF₃ 508 F Me 1 F H Cl H H CH₂CF₃ 509 F Me 0 Cl H Cl H H CH₂CF₃ 510 F Me 1 Cl H Cl H H CH₂CF₃ 511 F Me 0 Br H Cl H H CH₂CF₃ 512 F Me 1 Br H Cl H H CH₂CF₃ 513 F Me 0 I H Cl H H CH₂CF₃ 514 F Me 1 I H Cl H H CH₂CF₃ 515 F Me 0 CN H Cl H H CH₂CF₃ 516 F Me 1 CN H Cl H H CH₂CF₃ 517 F Me 0 NO₂ H Cl H H CH₂CF₃ 518 F Me 1 NO₂ H Cl H H CH₂CF₃ 519 F Me 0 NH₂ H Cl H H CH₂CF₃ 520 F Me 1 NH₂ H Cl H H CH₂CF₃ 521 F Me 0 CH₂OH H Cl H H CH₂CF₃ 522 F Me 1 CH₂OH H Cl H H CH₂CF₃ 523 F Me 0 COCH₃ H Cl H H CH₂CF₃ 524 F Me 1 COCH₃ H Cl H H CH₂CF₃ 525 F Me 0 COCH₂CH₃ H Cl H H CH₂CF₃ 526 F Me 1 COCH₂CH₃ H Cl H H CH₂CF₃ 527 F Me 0 COCH₂CH₂CH₃ H Cl H H CH₂CF₃ 528 F Me 1 COCH₂CH₂CH₃ H Cl H H CH₂CF₃ 529 F Me 0 COCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 530 F Me 1 COCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 531 F Me 0 COCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 532 F Me 1 COCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 533 F Me 0 COOH H Cl H H CH₂CF₃ 534 F Me 1 COOH H Cl H H CH₂CF₃ 535 F Me 0 CO₂CH₃ H Cl H H CH₂CF₃ 536 F Me 1 CO₂CH₃ H Cl H H CH₂CF₃ 537 F Me 0 CO₂CH₂CH₃ H Cl H H CH₂CF₃ 538 F Me 1 CO₂CH₂CH₃ H Cl H H CH₂CF₃ 539 F Me 0 CO₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 540 F Me 1 CO₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 541 F Me 0 CO₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 542 F Me 1 CO₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 543 F Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 544 F Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 545 F Me 0 CO₂CH(CH₃)₂ H Cl H H CH₂CF₃ 546 F Me 1 CO₂CH(CH₃)₂ H Cl H H CH₂CF₃ 547 F Me 0 CO₂CH₂CH(CH₃)₂ H Cl H H CH₂CF₃ 548 F Me 1 CO₂CH₂CH(CH₃)₂ H Cl H H CH₂CF₃ 549 F Me 0 CO₂CH═CH₂ H Cl H H CH₂CF₃ 550 F Me 1 CO₂CH═CH₂ H Cl H H CH₂CF₃ 551 F Me 0 CO₂CH₂CH═CH₂ H Cl H H CH₂CF₃ 552 F Me 1 CO₂CH₂CH═CH₂ H Cl H H CH₂CF₃ 553 F Me 0 CO₂CH₂CF₃ H Cl H H CH₂CF₃ 554 F Me 1 CO₂CH₂CF₃ H Cl H H CH₂CF₃ 555 F Me 0 CO₂CH₂CH₂Cl H Cl H H CH₂CF₃ 556 F Me 1 CO₂CH₂CH₂Cl H Cl H H CH₂CF₃ 557 F Me 0 CO₂CH₂CH₂Br H Cl H H CH₂CF₃ 558 F Me 1 CO₂CH₂CH₂Br H Cl H H CH₂CF₃ 559 F Me 0 CO₂CH₂OCH₃ H Cl H H CH₂CF₃ 560 F Me 1 CO₂CH₂COCH₃ H Cl H H CH₂CF₃ 561 F Me 0 CONH₂ H Cl H H CH₂CF₃ 562 F Me 1 CONH₂ H Cl H H CH₂CF₃ 563 F Me 0 CONHCH₃ H Cl H H CH₂CF₃ 564 F Me 1 CONHCH₃ H Cl H H CH₂CF₃ 565 F Me 0 CON(CH₃)₂ H Cl H H CH₂CF₃ 566 F Me 1 CON(CH₃)₂ H Cl H H CH₂CF₃ 567 F Me 0 CONHCH₂CH₃ H Cl H H CH₂CF₃ 568 F Me 1 CONHCH₂CH₃ H Cl H H CH₂CF₃ 569 F Me 0 CONHCH₂CH₂CH₃ H Cl H H CH₂CF₃ 570 F Me 1 CONHCH₂CH₂CH₃ H Cl H H CH₂CF₃ 571 F Me 0 CONHCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 572 F Me 1 CONHCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 573 F Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 574 F Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 575 F Me 0 OH H Cl H H CH₂CF₃ 576 F Me 1 OH H Cl H H CH₂CF₃ 577 F Me 0 OCH₃ H Cl H H CH₂CF₃ 578 F Me 1 OCH₃ H Cl H H CH₂CF₃ 579 F Me 0 OCH₂CH₃ H Cl H H CH₂CF₃ 580 F Me 1 OCH₂CH₃ H Cl H H CH₂CF₃ 581 F Me 0 OCH₂CH₂CH₃ H Cl H H CH₂CF₃ 582 F Me 1 OCH₂CH₂CH₃ H Cl H H CH₂CF₃ 583 F Me 0 OCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 584 F Me 1 OCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 585 F Me 0 OCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 586 F Me 1 SH H Cl H H CH₂CF₃ 587 F Me 0 SH H Cl H H CH₂CF₃ 588 F Me 1 SCH₃ H Cl H H CH₂CF₃ 589 F Me 0 SCH₃ H Cl H H CH₂CF₃ 590 F Me 1 SCH₂CH₃ H Cl H H CH₂CF₃ 591 F Me 0 SCH₂CH₃ H Cl H H CH₂CF₃ 592 F Me 1 SCH₂CH₂CH₃ H Cl H H CH₂CF₃ 593 F Me 0 SCH₂CH₂CH₃ H Cl H H CH₂CF₃ 594 F Me 1 SCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 595 F Me 0 SCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 596 F Me 1 SCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 597 Me Me 0 Me H Cl H H CH₂CF₃ 598 Me Me 1 Me H Cl H H CH₂CF₃ 599 Me Me 0 Et H Cl H H CH₂CF₃ 600 Me Me 1 Et H Cl H H CH₂CF₃ 601 Me Me 0 nPropyl H Cl H H CH₂CF₃ 602 Me Me 1 nPropyl H Cl H H CH₂CF₃ 603 Me Me 0 isopropyl H Cl H H CH₂CF₃ 604 Me Me 1 isopropyl H Cl H H CH₂CF₃ 605 Me Me 0 nButyl H Cl H H CH₂CF₃ 606 Me Me 1 nButyl H Cl H H CH₂CF₃ 607 Me Me 0 nPentyl H Cl H H CH₂CF₃ 608 Me Me 1 nPentyl H Cl H H CH₂CF₃ 609 Me Me 0 nHexyl H Cl H H CH₂CF₃ 610 Me Me 1 nHexyl H Cl H H CH₂CF₃ 611 Me Me 0 nHeptyl H Cl H H CH₂CF₃ 612 Me Me 1 nHeptyl H Cl H H CH₂CF₃ 613 Me Me 0 nOctyl H Cl H H CH₂CF₃ 614 Me Me 1 nOctyl H Cl H H CH₂CF₃ 615 Me Me 0 nNonyl H Cl H H CH₂CF₃ 616 Me Me 1 nNonyl H Cl H H CH₂CF₃ 617 Me Me 0 nDecyl H Cl H H CH₂CF₃ 618 Me Me 1 nDecyl H Cl H H CH₂CF₃ 619 Me Me 0 F H Cl H H CH₂CF₃ 620 Me Me 1 F H Cl H H CH₂CF₃ 621 Me Me 0 Cl H Cl H H CH₂CF₃ 622 Me Me 1 Cl H Cl H H CH₂CF₃ 623 Me Me 0 Br H Cl H H CH₂CF₃ 624 Me Me 1 Br H Cl H H CH₂CF₃ 625 Me Me 0 I H Cl H H CH₂CF₃ 626 Me Me 1 I H Cl H H CH₂CF₃ 627 Me Me 0 CN H Cl H H CH₂CF₃ 628 Me Me 1 CN H Cl H H CH₂CF₃ 629 Me Me 0 NO₂ H Cl H H CH₂CF₃ 630 Me Me 1 NO₂ H Cl H H CH₂CF₃ 631 Me Me 0 NH₂ H Cl H H CH₂CF₃ 632 Me Me 1 NH₂ H Cl H H CH₂CF₃ 633 Me Me 0 CH₂OH H Cl H H CH₂CF₃ 634 Me Me 1 CH₂OH H Cl H H CH₂CF₃ 635 Me Me 0 COCH₃ H Cl H H CH₂CF₃ 636 Me Me 1 COCH₃ H Cl H H CH₂CF₃ 637 Me Me 0 COCH₂CH₃ H Cl H H CH₂CF₃ 638 Me Me 1 COCH₂CH₃ H Cl H H CH₂CF₃ 639 Me Me 0 COCH₂CH₂CH₃ H Cl H H CH₂CF₃ 640 Me Me 1 COCH₂CH₂CH₃ H Cl H H CH₂CF₃ 641 Me Me 0 COCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 642 Me Me 1 COCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 643 Me Me 0 COCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 644 Me Me 1 COCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 645 Me Me 0 COOH H Cl H H CH₂CF₃ 646 Me Me 1 COOH H Cl H H CH₂CF₃ 647 Me Me 0 CO₂CH₃ H Cl H H CH₂CF₃ 648 Me Me 1 CO₂CH₃ H Cl H H CH₂CF₃ 649 Me Me 0 CO₂CH₂CH₃ H Cl H H CH₂CF₃ 650 Me Me 1 CO₂CH₂CH₃ H Cl H H CH₂CF₃ 651 Me Me 0 CO₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 652 Me Me 1 CO₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 653 Me Me 0 CO₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 654 Me Me 1 CO₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 655 Me Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 656 Me Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 657 Me Me 0 CO₂CH(CH₃)₂ H Cl H H CH₂CF₃ 658 Me Me 1 CO₂CH(CH₃)₂ H Cl H H CH₂CF₃ 659 Me Me 0 CO₂CH₂CH(CH₃)₂ H Cl H H CH₂CF₃ 660 Me Me 1 CO₂CH₂CH(CH₃)₂ H Cl H H CH₂CF₃ 661 Me Me 0 CO₂CH═CH₂ H Cl H H CH₂CF₃ 662 Me Me 1 CO₂CH═CH₂ H Cl H H CH₂CF₃ 663 Me Me 0 CO₂CH₂CH═CH₂ H Cl H H CH₂CF₃ 664 Me Me 1 CO₂CH₂CH═CH₂ H Cl H H CH₂CF₃ 665 Me Me 0 CO₂CH₂CF₃ H Cl H H CH₂CF₃ 666 Me Me 1 CO₂CH₂CF₃ H Cl H H CH₂CF₃ 667 Me Me 0 CO₂CH₂CH₂Cl H Cl H H CH₂CF₃ 668 Me Me 1 CO₂CH₂CH₂Cl H Cl H H CH₂CF₃ 669 Me Me 0 CO₂CH₂CH₂Br H Cl H H CH₂CF₃ 670 Me Me 1 CO₂CH₂CH₂Br H Cl H H CH₂CF₃ 671 Me Me 0 CO₂CH₂OCH₃ H Cl H H CH₂CF₃ 672 Me Me 1 CO₂CH₂COCH₃ H Cl H H CH₂CF₃ 673 Me Me 0 CONH₂ H Cl H H CH₂CF₃ 674 Me Me 1 CONH₂ H Cl H H CH₂CF₃ 675 Me Me 0 CONHCH₃ H Cl H H CH₂CF₃ 676 Me Me 1 CONHCH₃ H Cl H H CH₂CF₃ 677 Me Me 0 CON(CH₃)₂ H Cl H H CH₂CF₃ 678 Me Me 1 CON(CH₃)₂ H Cl H H CH₂CF₃ 679 Me Me 0 CONHCH₂CH₃ H Cl H H CH₂CF₃ 680 Me Me 1 CONHCH₂CH₃ H Cl H H CH₂CF₃ 681 Me Me 0 CONHCH₂CH₂CH₃ H Cl H H CH₂CF₃ 682 Me Me 1 CONHCH₂CH₂CH₃ H Cl H H CH₂CF₃ 683 Me Me 0 CONHCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 684 Me Me 1 CONHCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 685 Me Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 686 Me Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 687 Me Me 0 OH H Cl H H CH₂CF₃ 688 Me Me 1 OH H Cl H H CH₂CF₃ 689 Me Me 0 OCH₃ H Cl H H CH₂CF₃ 690 Me Me 1 OCH₃ H Cl H H CH₂CF₃ 691 Me Me 0 OCH₂CH₃ H Cl H H CH₂CF₃ 692 Me Me 1 OCH₂CH₃ H Cl H H CH₂CF₃ 693 Me Me 0 OCH₂CH₂CH₃ H Cl H H CH₂CF₃ 694 Me Me 1 OCH₂CH₂CH₃ H Cl H H CH₂CF₃ 695 Me Me 0 OCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 696 Me Me 1 OCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 697 Me Me 0 OCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 698 Me Me 1 SH H Cl H H CH₂CF₃ 699 Me Me 0 SH H Cl H H CH₂CF₃ 700 Me Me 1 SCH₃ H Cl H H CH₂CF₃ 701 Me Me 0 SCH₃ H Cl H H CH₂CF₃ 702 Me Me 1 SCH₂CH₃ H Cl H H CH₂CF₃ 703 Me Me 0 SCH₂CH₃ H Cl H H CH₂CF₃ 704 Me Me 1 SCH₂CH₂CH₃ H Cl H H CH₂CF₃ 705 Me Me 0 SCH₂CH₂CH₃ H Cl H H CH₂CF₃ 706 Me Me 1 SCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 707 Me Me 0 SCH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 708 Me Me 1 SCH₂CH₂CH₂CH₂CH₃ H Cl H H CH₂CF₃ 709 F Me 0 H H F H H CH₂CF₃ 710 F Me 1 H H F H H CH₂CF₃ 711 F Me 0 H H Cl H H CH₂CF₃ 712 F Me 1 H H Cl H H CH₂CF₃ 713 F Me 0 H H Br H H CH₂CF₃ 714 F Me 1 H H Br H H CH₂CF₃ 715 F Me 0 H H I H H CH₂CF₃ 716 F Me 1 H H I H H CH₂CF₃ 717 F Me 0 H H OH H H CH₂CF₃ 718 F Me 1 H H OH H H CH₂CF₃ 719 F Me 0 H H NH₂ H H CH₂CF₃ 720 F Me 1 H H NH₂ H H CH₂CF₃ 721 F Me 0 H H CN H H CH₂CF₃ 722 F Me 1 H H CN H H CH₂CF₃ 723 F Me 0 H H NO₂ H H CH₂CF₃ 724 F Me 1 H H NO₂ H H CH₂CF₃ 725 F Me 0 H H CF₃ H H CH₂CF₃ 726 F Me 1 H H CF₃ H H CH₂CF₃ 727 F Me 0 H H COCH₃ H H CH₂CF₃ 728 F Me 1 H H COCH₃ H H CH₂CF₃ 729 F Me 0 H H COCH₂CH₃ H H CH₂CF₃ 730 F Me 1 H H COCH₂CH₃ H H CH₂CF₃ 731 F Me 0 H H COCH₂CH₂CH₃ H H CH₂CF₃ 732 F Me 1 H H COCH₂CH₂CH₃ H H CH₂CF₃ 733 F Me 0 H H COCH₂CH₂CH₂CH₃ H H CH₂CF₃ 734 F Me 1 H H COCH₂CH₂CH₂CH₃ H H CH₂CF₃ 735 F Me 0 H H COCH₂CH₂CH₂CH₂CH₃ H H CH₂CF₃ 736 F Me 1 H H COCH₂CH₂CH₂CH₂CH₃ H H CH₂CF₃ 737 F Me 0 H H COOH H H CH₂CF₃ 738 F Me 1 H H COOH H H CH₂CF₃ 739 F Me 0 H H CO₂CH₃ H H CH₂CF₃ 740 F Me 1 H H CO₂CH₃ H H CH₂CF₃ 741 F Me 0 H H F H H CH₂CF₃ 742 F Me 1 H H F H H CH₂CF₃ 743 F Me 0 H H Cl H H CH₂CF₃ 744 F Me 1 H H Cl H H CH₂CF₃ 745 F Me 0 H H Br H H CH₂CF₃ 746 F Me 1 H H Br H H CH₂CF₃ 747 F Me 0 H H I H H CH₂CF₃ 748 F Me 1 H H I H H CH₂CF₃ 749 F Me 0 H H OH H H CH₂CF₃ 750 F Me 1 H H OH H H CH₂CF₃ 751 F Me 0 H H NH₂ H H CH₂CF₃ 752 F Me 1 H H NH₂ H H CH₂CF₃ 753 F Me 0 H H CN H H CH₂CF₃ 754 F Me 1 H H CN H H CH₂CF₃ 755 F Me 0 H H NO₂ H H CH₂CF₃ 756 F Me 1 H H NO₂ H H CH₂CF₃ 757 F Me 0 H H COCH₃ H H CH₂CF₃ 758 F Me 1 H H COCH₃ H H CH₂CF₃ 759 F Me 0 H H COCH₂CH₃ H H CH₂CF₃ 760 F Me 1 H H COCH₂CH₃ H H CH₂CF₃ 761 F Me 0 H H COCH₂CH₂CH₃ H H CH₂CF₃ 762 F Me 1 H H COCH₂CH₂CH₃ H H CH₂CF₃ 763 F Me 0 H H COCH₂CH₂CH₂CH₃ H H CH₂CF₃ 764 F Me 1 H H COCH₂CH₂CH₂CH₃ H H CH₂CF₃ 765 F Me 0 H H COCH₂CH₂CH₂CH₂CH₃ H H CH₂CF₃ 766 F Me 1 H H COCH₂CH₂CH₂CH₂CH₃ H H CH₂CF₃ 767 F Me 0 Me H H H H nPropyl 768 F Me 1 Me H H H H nPropyl 769 F Me 0 Et H H H H nPropyl 770 F Me 1 Et H H H H nPropyl 771 F Me 0 nPropyl H H H H nPropyl 772 F Me 1 nPropyl H H H H nPropyl 773 F Me 0 isopropyl H H H H nPropyl 774 F Me 1 isopropyl H H H H nPropyl 775 F Me 0 nButyl H H H H nPropyl 776 F Me 1 nButyl H H H H nPropyl 777 F Me 0 nPentyl H H H H nPropyl 778 F Me 1 nPentyl H H H H nPropyl 779 F Me 0 nHexyl H H H H nPropyl 780 F Me 1 nHexyl H H H H nPropyl 781 F Me 0 nHeptyl H H H H nPropyl 782 F Me 1 nHeptyl H H H H nPropyl 783 F Me 0 nOctyl H H H H nPropyl 784 F Me 1 nOctyl H H H H nPropyl 785 F Me 0 nNonyl H H H H nPropyl 786 F Me 1 nNonyl H H H H nPropyl 787 F Me 0 nDecyl H H H H nPropyl 788 F Me 1 nDecyl H H H H nPropyl 789 F Me 0 F H H H H nPropyl 790 F Me 1 F H H H H nPropyl 791 F Me 0 Cl H H H H nPropyl 792 F Me 1 Cl H H H H nPropyl 793 F Me 0 Br H H H H nPropyl 794 F Me 1 Br H H H H nPropyl 795 F Me 0 I H H H H nPropyl 796 F Me 1 I H H H H nPropyl 797 F Me 0 CN H H H H nPropyl 798 F Me 1 CN H H H H nPropyl 799 F Me 0 NO₂ H H H H nPropyl 800 F Me 1 NO₂ H H H H nPropyl 801 F Me 0 NH₂ H H H H nPropyl 802 F Me 1 NH₂ H H H H nPropyl 803 F Me 0 CH₂OH H H H H nPropyl 804 F Me 1 CH₂OH H H H H nPropyl 805 F Me 0 COCH₃ H H H H nPropyl 806 F Me 1 COCH₃ H H H H nPropyl 807 F Me 0 COCH₂CH₃ H H H H nPropyl 808 F Me 1 COCH₂CH₃ H H H H nPropyl 809 F Me 0 COCH₂CH₂CH₃ H H H H nPropyl 810 F Me 1 COCH₂CH₂CH₃ H H H H nPropyl 811 F Me 0 COCH₂CH₂CH₂CH₃ H H H H nPropyl 812 F Me 1 COCH₂CH₂CH₂CH₃ H H H H nPropyl 813 F Me 0 COCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 814 F Me 1 COCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 815 F Me 0 COOH H H H H nPropyl 816 F Me 1 COOH H H H H nPropyl 817 F Me 0 CO₂CH₃ H H H H nPropyl 818 F Me 1 CO₂CH₃ H H H H nPropyl 819 F Me 0 CO₂CH₂CH₃ H H H H nPropyl 820 F Me 1 CO₂CH₂CH₃ H H H H nPropyl 821 F Me 0 CO₂CH₂CH₂CH₃ H H H H nPropyl 822 F Me 1 CO₂CH₂CH₂CH₃ H H H H nPropyl 823 F Me 0 CO₂CH₂CH₂CH₂CH₃ H H H H nPropyl 824 F Me 1 CO₂CH₂CH₂CH₂CH₃ H H H H nPropyl 825 F Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 826 F Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 827 F Me 0 CO₂CH(CH₃)₂ H H H H nPropyl 828 F Me 1 CO₂CH(CH₃)₂ H H H H nPropyl 829 F Me 0 CO₂CH₂CH(CH₃)₂ H H H H nPropyl 830 F Me 1 CO₂CH₂CH(CH₃)₂ H H H H nPropyl 831 F Me 0 CO₂CH═CH₂ H H H H nPropyl 832 F Me 1 CO₂CH═CH₂ H H H H nPropyl 833 F Me 0 CO₂CH₂CH═CH₂ H H H H nPropyl 834 F Me 1 CO₂CH₂CH═CH₂ H H H H nPropyl 835 F Me 0 CO₂CH₂CF₃ H H H H nPropyl 836 F Me 1 CO₂CH₂CF₃ H H H H nPropyl 837 F Me 0 CO₂CH₂CH₂Cl H H H H nPropyl 838 F Me 1 CO₂CH₂CH₂Cl H H H H nPropyl 839 F Me 0 CO₂CH₂CH₂Br H H H H nPropyl 840 F Me 1 CO₂CH₂CH₂Br H H H H nPropyl 841 F Me 0 CO₂CH₂OCH₃ H H H H nPropyl 842 F Me 1 CO₂CH₂COCH₃ H H H H nPropyl 843 F Me 0 CONH₂ H H H H nPropyl 844 F Me 1 CONH₂ H H H H nPropyl 845 F Me 0 CONHCH₃ H H H H nPropyl 846 F Me 1 CONHCH₃ H H H H nPropyl 847 F Me 0 CON(CH₃)₂ H H H H nPropyl 848 F Me 1 CON(CH₃)₂ H H H H nPropyl 849 F Me 0 CONHCH₂CH₃ H H H H nPropyl 850 F Me 1 CONHCH₂CH₃ H H H H nPropyl 851 F Me 0 CONHCH₂CH₂CH₃ H H H H nPropyl 852 F Me 1 CONHCH₂CH₂CH₃ H H H H nPropyl 853 F Me 0 CONHCH₂CH₂CH₂CH₃ H H H H nPropyl 854 F Me 1 CONHCH₂CH₂CH₂CH₃ H H H H nPropyl 855 F Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 856 F Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 857 F Me 0 OH H H H H nPropyl 858 F Me 1 OH H H H H nPropyl 859 F Me 0 OCH₃ H H H H nPropyl 860 F Me 1 OCH₃ H H H H nPropyl 861 F Me 0 OCH₂CH₃ H H H H nPropyl 862 F Me 1 OCH₂CH₃ H H H H nPropyl 863 F Me 0 OCH₂CH₂CH₃ H H H H nPropyl 864 F Me 1 OCH₂CH₂CH₃ H H H H nPropyl 865 F Me 0 OCH₂CH₂CH₂CH₃ H H H H nPropyl 866 F Me 1 OCH₂CH₂CH₂CH₃ H H H H nPropyl 867 F Me 0 OCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 868 F Me 1 SH H H H H nPropyl 869 F Me 0 SH H H H H nPropyl 870 F Me 1 SCH₃ H H H H nPropyl 871 F Me 0 SCH₃ H H H H nPropyl 872 F Me 1 SCH₂CH₃ H H H H nPropyl 873 F Me 0 SCH₂CH₃ H H H H nPropyl 874 F Me 1 SCH₂CH₂CH₃ H H H H nPropyl 875 F Me 0 SCH₂CH₂CH₃ H H H H nPropyl 876 F Me 1 SCH₂CH₂CH₂CH₃ H H H H nPropyl 877 F Me 0 SCH₂CH₂CH₂CH₃ H H H H nPropyl 878 F Me 1 SCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 879 Me Me 0 Me H H H H nPropyl 880 Me Me 1 Me H H H H nPropyl 881 Me Me 0 Et H H H H nPropyl 882 Me Me 1 Et H H H H nPropyl 883 Me Me 0 nPropyl H H H H nPropyl 884 Me Me 1 nPropyl H H H H nPropyl 885 Me Me 0 isopropyl H H H H nPropyl 886 Me Me 1 isopropyl H H H H nPropyl 887 Me Me 0 nButyl H H H H nPropyl 888 Me Me 1 nButyl H H H H nPropyl 889 Me Me 0 nPentyl H H H H nPropyl 890 Me Me 1 nPentyl H H H H nPropyl 891 Me Me 0 nHexyl H H H H nPropyl 892 Me Me 1 nHexyl H H H H nPropyl 893 Me Me 0 nHeptyl H H H H nPropyl 894 Me Me 1 nHeptyl H H H H nPropyl 895 Me Me 0 nOctyl H H H H nPropyl 896 Me Me 1 nOctyl H H H H nPropyl 897 Me Me 0 nNonyl H H H H nPropyl 898 Me Me 1 nNonyl H H H H nPropyl 899 Me Me 0 nDecyl H H H H nPropyl 900 Me Me 1 nDecyl H H H H nPropyl 901 Me Me 0 F H H H H nPropyl 902 Me Me 1 F H H H H nPropyl 903 Me Me 0 Cl H H H H nPropyl 904 Me Me 1 Cl H H H H nPropyl 905 Me Me 0 Br H H H H nPropyl 906 Me Me 1 Br H H H H nPropyl 907 Me Me 0 I H H H H nPropyl 908 Me Me 1 I H H H H nPropyl 909 Me Me 0 CN H H H H nPropyl 910 Me Me 1 CN H H H H nPropyl 911 Me Me 0 NO₂ H H H H nPropyl 912 Me Me 1 NO₂ H H H H nPropyl 913 Me Me 0 NH₂ H H H H nPropyl 914 Me Me 1 NH₂ H H H H nPropyl 915 Me Me 0 CH₂OH H H H H nPropyl 916 Me Me 1 CH₂OH H H H H nPropyl 917 Me Me 0 COCH₃ H H H H nPropyl 918 Me Me 1 COCH₃ H H H H nPropyl 919 Me Me 0 COCH₂CH₃ H H H H nPropyl 920 Me Me 1 COCH₂CH₃ H H H H nPropyl 921 Me Me 0 COCH₂CH₂CH₃ H H H H nPropyl 922 Me Me 1 COCH₂CH₂CH₃ H H H H nPropyl 923 Me Me 0 COCH₂CH₂CH₂CH₃ H H H H nPropyl 924 Me Me 1 COCH₂CH₂CH₂CH₃ H H H H nPropyl 925 Me Me 0 COCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 926 Me Me 1 COCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 927 Me Me 0 COOH H H H H nPropyl 928 Me Me 1 COOH H H H H nPropyl 929 Me Me 0 CO₂CH₃ H H H H nPropyl 930 Me Me 1 CO₂CH₃ H H H H nPropyl 931 Me Me 0 CO₂CH₂CH₃ H H H H nPropyl 932 Me Me 1 CO₂CH₂CH₃ H H H H nPropyl 933 Me Me 0 CO₂CH₂CH₂CH₃ H H H H nPropyl 934 Me Me 1 CO₂CH₂CH₂CH₃ H H H H nPropyl 935 Me Me 0 CO₂CH₂CH₂CH₂CH₃ H H H H nPropyl 936 Me Me 1 CO₂CH₂CH₂CH₂CH₃ H H H H nPropyl 937 Me Me 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 938 Me Me 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 939 Me Me 0 CO₂CH(CH₃)₂ H H H H nPropyl 940 Me Me 1 CO₂CH(CH₃)₂ H H H H nPropyl 941 Me Me 0 CO₂CH₂CH(CH₃)₂ H H H H nPropyl 942 Me Me 1 CO₂CH₂CH(CH₃)₂ H H H H nPropyl 943 Me Me 0 CO₂CH═CH₂ H H H H nPropyl 944 Me Me 1 CO₂CH═CH₂ H H H H nPropyl 945 Me Me 0 CO₂CH₂CH═CH₂ H H H H nPropyl 946 Me Me 1 CO₂CH₂CH═CH₂ H H H H nPropyl 947 Me Me 0 CO₂CH₂CF₃ H H H H nPropyl 948 Me Me 1 CO₂CH₂CF₃ H H H H nPropyl 949 Me Me 0 CO₂CH₂CH₂Cl H H H H nPropyl 950 Me Me 1 CO₂CH₂CH₂Cl H H H H nPropyl 951 Me Me 0 CO₂CH₂CH₂Br H H H H nPropyl 952 Me Me 1 CO₂CH₂CH₂Br H H H H nPropyl 953 Me Me 0 CO₂CH₂OCH₃ H H H H nPropyl 954 Me Me 1 CO₂CH₂COCH₃ H H H H nPropyl 955 Me Me 0 CONH₂ H H H H nPropyl 956 Me Me 1 CONH₂ H H H H nPropyl 957 Me Me 0 CONHCH₃ H H H H nPropyl 958 Me Me 1 CONHCH₃ H H H H nPropyl 959 Me Me 0 CON(CH₃)₂ H H H H nPropyl 960 Me Me 1 CON(CH₃)₂ H H H H nPropyl 961 Me Me 0 CONHCH₂CH₃ H H H H nPropyl 962 Me Me 1 CONHCH₂CH₃ H H H H nPropyl 963 Me Me 0 CONHCH₂CH₂CH₃ H H H H nPropyl 964 Me Me 1 CONHCH₂CH₂CH₃ H H H H nPropyl 965 Me Me 0 CONHCH₂CH₂CH₂CH₃ H H H H nPropyl 966 Me Me 1 CONHCH₂CH₂CH₂CH₃ H H H H nPropyl 967 Me Me 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 968 Me Me 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 969 Me Me 0 OH H H H H nPropyl 970 Me Me 1 OH H H H H nPropyl 971 Me Me 0 OCH₃ H H H H nPropyl 972 Me Me 1 OCH₃ H H H H nPropyl 973 Me Me 0 OCH₂CH₃ H H H H nPropyl 974 Me Me 1 OCH₂CH₃ H H H H nPropyl 975 Me Me 0 OCH₂CH₂CH₃ H H H H nPropyl 976 Me Me 1 OCH₂CH₂CH₃ H H H H nPropyl 977 Me Me 0 OCH₂CH₂CH₂CH₃ H H H H nPropyl 978 Me Me 1 OCH₂CH₂CH₂CH₃ H H H H nPropyl 979 Me Me 0 OCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 980 Me Me 1 SH H H H H nPropyl 981 Me Me 0 SH H H H H nPropyl 982 Me Me 1 SCH₃ H H H H nPropyl 983 Me Me 0 SCH₃ H H H H nPropyl 984 Me Me 1 SCH₂CH₃ H H H H nPropyl 985 Me Me 0 SCH₂CH₃ H H H H nPropyl 986 Me Me 1 SCH₂CH₂CH₃ H H H H nPropyl 987 Me Me 0 SCH₂CH₂CH₃ H H H H nPropyl 988 Me Me 1 SCH₂CH₂CH₂CH₃ H H H H nPropyl 989 Me Me 0 SCH₂CH₂CH₂CH₃ H H H H nPropyl 990 Me Me 1 SCH₂CH₂CH₂CH₂CH₃ H H H H nPropyl 991 F Me 0 Me H H H H CH₂CF₃ 992 F Me 1 Me H H H H CH₂CF₃ 993 F Me 0 CF₃ H H H H CH₂CF₃ 994 F Me 1 CF₃ H H H H CH₂CF₃ 995 F Me 0 Et H H H H CH₂CF₃ 996 F Me 1 Et H H H H CH₂CF₃ 997 F Me 0 nPropyl H H H H CH₂CF₃ 998 F Me 1 nPropyl H H H H CH₂CF₃ 999 F Me 0 isopropyl H H H H CH₂CF₃ 1000 F Me 1 isopropyl H H H H CH₂CF₃ 1001 F Me 0 nButyl H H H H CH₂CF₃ 1002 F Me 1 nButyl H H H H CH₂CF₃ 1003 F Me 0 nPentyl H H H H CH₂CF₃ 1004 F Me 1 nPentyl H H H H CH₂CF₃ 1005 F Me 0 nHexyl H H H H CH₂CF₃ 1006 F Me 1 nHexyl H H H H CH₂CF₃ 1007 F Me 0 nHeptyl H H H H CH₂CF₃ 1008 F Me 1 nHeptyl H H H H CH₂CF₃ 1009 F Me 0 nOctyl H H H H CH₂CF₃ 1010 F Me 1 nOctyl H H H H CH₂CF₃ 1011 F Me 0 nNonyl H H H H CH₂CF₃ 1012 F Me 1 nNonyl H H H H CH₂CF₃ 1013 F Me 0 nDecyl H H H H CH₂CF₃ 1014 F Me 1 nDecyl H H H H CH₂CF₃ 1015 F Me 0 F H H H H CH₂CF₃ 1016 F Me 1 F H H H H CH₂CF₃ 1017 F Me 0 Cl H H H H CH₂CF₃ 1018 F Me 1 Cl H H H H CH₂CF₃ 1019 F Me 0 Br H H H H CH₂CF₃ 1020 F Me 1 Br H H H H CH₂CF₃ 1021 F Me 0 I H H H H CH₂CF₃ 1022 F Me 1 I H H H H CH₂CF₃ 1023 F Me 0 CN H H H H CH₂CF₃ 1024 F Me 1 CN H H H H CH₂CF₃ 1025 F Me 0 NO₂ H H H H CH₂CF₃ 1026 F Me 1 NO₂ H H H H CH₂CF₃ 1027 F Me 0 NH₂ H H H H CH₂CF₃ 1028 F Me 1 NH₂ H H H H CH₂CF₃ 1029 F Me 0 CH₂OH H H H H CH₂CF₃ 1030 Cl Cl 1 CH₂OH H H H H CH₂CF₃ 1031 Cl Cl 0 COCH₃ H H H H CH₂CF₃ 1032 Cl Cl 1 COCH₃ H H H H CH₂CF₃ 1033 Cl Cl 0 COCH₂CH₃ H H H H CH₂CF₃ 1034 Cl Cl 1 COCH₂CH₃ H H H H CH₂CF₃ 1035 Cl Cl 0 COCH₂CH₂CH₃ H H H H CH₂CF₃ 1036 Cl Cl 1 COCH₂CH₂CH₃ H H H H CH₂CF₃ 1037 Cl Cl 0 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1038 Cl Cl 1 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1039 Cl Cl 0 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1040 Cl Cl 1 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1041 Cl Cl 0 COOH H H H H CH₂CF₃ 1042 Cl Cl 1 COOH H H H H CH₂CF₃ 1043 Cl Cl 0 CO₂CH₃ H H H H CH₂CF₃ 1044 Cl Cl 1 CO₂CH₃ H H H H CH₂CF₃ 1045 Cl Cl 0 CO₂CH₂CH₃ H H H H CH₂CF₃ 1046 Cl Cl 1 CO₂CH₂CH₃ H H H H CH₂CF₃ 1047 Cl Cl 0 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1048 Cl Cl 1 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1049 Cl Cl 0 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1050 Cl Cl 1 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1051 Cl Cl 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1052 Cl Cl 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1053 Cl Cl 0 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 1054 Cl Cl 1 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 1055 Cl Cl 0 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 1056 Cl Cl 1 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 1057 Cl Cl 0 CO₂CH═CH₂ H H H H CH₂CF₃ 1058 Cl Cl 1 CO₂CH═CH₂ H H H H CH₂CF₃ 1059 Cl Cl 0 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 1060 Cl Cl 1 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 1061 Cl Cl 0 CO₂CH₂CF₃ H H H H CH₂CF₃ 1062 Cl Cl 1 CO₂CH₂CF₃ H H H H CH₂CF₃ 1063 Cl Cl 0 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 1064 Cl Cl 1 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 1065 Cl Cl 0 CO₂CH₂CH₂Br H H H H CH₂CF₃ 1066 Cl Cl 1 CO₂CH₂CH₂Br H H H H CH₂CF₃ 1067 Cl Cl 0 CO₂CH₂OCH₃ H H H H CH₂CF₃ 1068 Cl Cl 1 CO₂CH₂COCH₃ H H H H CH₂CF₃ 1069 Cl Cl 0 CONH₂ H H H H CH₂CF₃ 1070 Cl Cl 1 CONH₂ H H H H CH₂CF₃ 1071 Cl Cl 0 CONHCH₃ H H H H CH₂CF₃ 1072 Cl Cl 1 CONHCH₃ H H H H CH₂CF₃ 1073 Cl Cl 0 CON(CH₃)₂ H H H H CH₂CF₃ 1074 Cl Cl 1 CON(CH₃)₂ H H H H CH₂CF₃ 1075 Cl Cl 0 CONHCH₂CH₃ H H H H CH₂CF₃ 1076 Cl Cl 1 CONHCH₂CH₃ H H H H CH₂CF₃ 1077 Cl Cl 0 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 1078 Cl Cl 1 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 1079 Cl Cl 0 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1080 Cl Cl 1 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1081 Cl Cl 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1082 Cl Cl 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1083 Cl Cl 0 OH H H H H CH₂CF₃ 1084 Cl Cl 1 OH H H H H CH₂CF₃ 1085 Cl Cl 0 OCH₃ H H H H CH₂CF₃ 1086 Cl Cl 1 OCH₃ H H H H CH₂CF₃ 1087 Cl Cl 0 OCH₂CH₃ H H H H CH₂CF₃ 1088 Cl Cl 1 OCH₂CH₃ H H H H CH₂CF₃ 1089 Cl Cl 0 OCH₂CH₂CH₃ H H H H CH₂CF₃ 1090 Cl Cl 1 OCH₂CH₂CH₃ H H H H CH₂CF₃ 1091 Cl Cl 0 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1092 Cl Cl 1 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1093 Cl Cl 0 OCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1094 Cl Cl 1 SH H H H H CH₂CF₃ 1095 Cl Cl 0 SH H H H H CH₂CF₃ 1096 Cl Cl 1 SCH₃ H H H H CH₂CF₃ 1097 Cl Cl 0 SCH₃ H H H H CH₂CF₃ 1098 Cl Cl 1 SCH₂CH₃ H H H H CH₂CF₃ 1099 Cl Cl 0 SCH₂CH₃ H H H H CH₂CF₃ 1100 Cl Cl 1 SCH₂CH₂CH₃ H H H H CH₂CF₃ 1101 Cl Cl 0 SCH₂CH₂CH₃ H H H H CH₂CF₃ 1102 Cl Cl 1 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1103 Cl Cl 0 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1104 Cl Cl 1 SCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1105 F Me 0 H H H H H CH₂CF₃ 1106 F Me 1 H H H H H CH₂CF₃ 1107 F Me 0 OCF3 H H H H CH₂CF₃ 1108 F Me 1 OCF3 H H H H CH₂CF₃ 1109 F Me 0 H H OCH₃ H H CH₂CF₃ 1110 F Me 1 H H OCH₃ H H CH₂CF₃ 1111 F Me 0 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1112 F Me 1 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1113 F Me 0 CO₂CH₃ H F H H nPropyl 1114 F Me 1 CO₂CH₃ H F H H nPropyl 1115 F Me 0 CO₂CH₃ H Cl H H nPropyl 1116 F Me 1 CO₂CH₃ H Cl H H nPropyl 1117 F Me 0 CO₂CH₃ H Br H H CH₂CF₃ 1118 F Me 1 CO₂CH₃ H Br H H CH₂CF₃ 1119 F Me 0 CO₂CH₃ H I H H CH₂CF₃ 1120 F Me 1 CO₂CH₃ H I H H CH₂CF₃ 1121 F Me 0 CO₂CH₃ H OH H H CH₂CF₃ 1122 F Me 1 CO₂CH₃ H OH H H CH₂CF₃ 1123 F Me 0 CO₂CH₃ H NH₂ H H CH₂CF₃ 1124 F Me 1 CO₂CH₃ H NH₂ H H CH₂CF₃ 1125 F Me 0 CO₂CH₃ H CN H H CH₂CF₃ 1126 F Me 1 CO₂CH₃ H CN H H CH₂CF₃ 1127 F Me 0 CO₂CH₃ H NO₂ H H CH₂CF₃ 1128 F Me 1 CO₂CH₃ H NO₂ H H CH₂CF₃ 1129 F Me 0 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1130 F Me 1 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1131 F Me 0 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1132 F Me 1 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1133 F Me 0 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1134 F Me 1 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1135 F Me 0 CO₂CH₃ H OPh H H CH₂CF₃ 1136 F Me 1 CO₂CH₃ H OPh H H CH₂CF₃ 1137 Me Me 0 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1138 Me Me 1 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1139 Me Me 0 CO₂CH₃ H F H H CH₂CF₃ 1140 Me Me 1 CO₂CH₃ H F H H CH₂CF₃ 1141 Me Me 0 CO₂CH₃ H Cl H H CH₂CF₃ 1142 Me Me 1 CO₂CH₃ H Cl H H CH₂CF₃ 1143 Me Me 0 CO₂CH₃ H Br H H CH₂CF₃ 1144 Me Me 1 CO₂CH₃ H Br H H CH₂CF₃ 1145 Me Me 0 CO₂CH₃ H I H H CH₂CF₃ 1146 Me Me 1 CO₂CH₃ H I H H CH₂CF₃ 1147 Me Me 0 CO₂CH₃ H OH H H CH₂CF₃ 1148 Me Me 1 CO₂CH₃ H OH H H CH₂CF₃ 1149 Me Me 0 CO₂CH₃ H NH₂ H H CH₂CF₃ 1150 Me Me 1 CO₂CH₃ H NH₂ H H CH₂CF₃ 1151 Me Me 0 CO₂CH₃ H CN H H CH₂CF₃ 1152 Me Me 1 CO₂CH₃ H CN H H CH₂CF₃ 1153 Me Me 0 CO₂CH₃ H NO₂ H H CH₂CF₃ 1154 Me Me 1 CO₂CH₃ H NO₂ H H CH₂CF₃ 1155 Me Me 0 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1156 Me Me 1 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1157 Me Me 0 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1158 Me Me 1 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1159 Me Me 0 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1160 Me Me 1 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1161 Me Me 0 CO₂CH₃ H OPh H H CH₂CF₃ 1162 Me Me 1 CO₂CH₃ H OPh H H CH₂CF₃ 1163 F Cl 0 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1164 F Cl 1 CO₂CH₃ H CO₂CH₃ H H CH₂CF₃ 1165 F Cl 0 CO₂CH₃ H F H H CH₂CF₃ 1166 F Cl 1 CO₂CH₃ H F H H CH₂CF₃ 1167 F Cl 0 CO₂CH₃ H Cl H H CH₂CF₃ 1168 F Cl 1 CO₂CH₃ H Cl H H CH₂CF₃ 1169 F Cl 0 CO₂CH₃ H Br H H CH₂CF₃ 1170 F Cl 1 CO₂CH₃ H Br H H CH₂CF₃ 1171 F Cl 0 CO₂CH₃ H I H H CH₂CF₃ 1172 F Cl 1 CO₂CH₃ H I H H CH₂CF₃ 1173 F Cl 0 CO₂CH₃ H OH H H CH₂CF₃ 1174 F Cl 1 CO₂CH₃ H OH H H CH₂CF₃ 1175 F Cl 0 CO₂CH₃ H NH₂ H H CH₂CF₃ 1176 F Cl 1 CO₂CH₃ H NH₂ H H CH₂CF₃ 1177 F Cl 0 CO₂CH₃ H CN H H CH₂CF₃ 1178 F Cl 1 CO₂CH₃ H CN H H CH₂CF₃ 1179 F Cl 0 CO₂CH₃ H NO₂ H H CH₂CF₃ 1180 F Cl 1 CO₂CH₃ H NO₂ H H CH₂CF₃ 1181 F Cl 0 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1182 F Cl 1 CO₂CH₃ H COCH₃ H H CH₂CF₃ 1183 F Cl 0 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1184 F Cl 1 CO₂CH₃ H OCH₃ H H CH₂CF₃ 1185 F Cl 0 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1186 F Cl 1 CO₂CH₃ H OCH₂CH₃ H H CH₂CF₃ 1187 F Cl 0 CO₂CH₃ H OPh H H CH₂CF₃ 1188 F Cl 1 CO₂CH₃ H OPh H H CH₂CF₃ 1189 F Cl 1 CH₂OH H H H H CH₂CF₃ 1190 F Cl 0 COCH₃ H H H H CH₂CF₃ 1191 F Cl 1 COCH₃ H H H H CH₂CF₃ 1192 F Cl 0 COCH₂CH₃ H H H H CH₂CF₃ 1193 F Cl 1 COCH₂CH₃ H H H H CH₂CF₃ 1194 F Cl 0 COCH₂CH₂CH₃ H H H H CH₂CF₃ 1195 F Cl 1 COCH₂CH₂CH₃ H H H H CH₂CF₃ 1196 F Cl 0 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1197 F Cl 1 COCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1198 F Cl 0 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1199 F Cl 1 COCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1200 F Cl 0 COOH H H H H CH₂CF₃ 1201 F Cl 1 COOH H H H H CH₂CF₃ 1202 F Cl 0 CO₂CH₃ H H H H CH₂CF₃ 1203 F Cl 1 CO₂CH₃ H H H H CH₂CF₃ 1204 F Cl 0 CO₂CH₂CH₃ H H H H CH₂CF₃ 1205 F Cl 1 CO₂CH₂CH₃ H .H H H CH₂CF₃ 1206 F Cl 0 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1207 F Cl 1 CO₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1208 F Cl 0 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1209 F Cl 1 CO₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1210 F Cl 0 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1211 F Cl 1 CO₂CH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1212 F Cl 0 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 1213 F Cl 1 CO₂CH(CH₃)₂ H H H H CH₂CF₃ 1214 F Cl 0 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 1215 F Cl 1 CO₂CH₂CH(CH₃)₂ H H H H CH₂CF₃ 1216 F Cl 0 CO₂CH═CH₂ H H H H CH₂CF₃ 1217 F Cl 1 CO₂CH═CH₂ H H H H CH₂CF₃ 1218 F Cl 0 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 1219 F Cl 1 CO₂CH₂CH═CH₂ H H H H CH₂CF₃ 1220 F Cl 0 CO₂CH₂CF₃ H H H H CH₂CF₃ 1221 F Cl 1 CO₂CH₂CF₃ H H H H CH₂CF₃ 1222 F Cl 0 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 1223 F Cl 1 CO₂CH₂CH₂Cl H H H H CH₂CF₃ 1224 F Cl 0 CO₂CH₂CH₂Br H H H H CH₂CF₃ 1225 F Cl 1 CO₂CH₂CH₂Br H H H H CH₂CF₃ 1226 F Cl 0 CO₂CH₂OCH₃ H H H H CH₂CF₃ 1227 F Cl 1 CO₂CH₂COCH₃ H H H H CH₂CF₃ 1228 F Cl 0 CONH₂ H H H H CH₂CF₃ 1229 F Cl 1 CONH₂ H H H H CH₂CF₃ 1230 F Cl 0 CONHCH₃ H H H H CH₂CF₃ 1231 F Cl 1 CONHCH₃ H H H H CH₂CF₃ 1232 F Cl 0 CON(CH₃)₂ H H H H CH₂CF₃ 1233 F Cl 1 CON(CH₃)₂ H H H H CH₂CF₃ 1234 F Cl 0 CONHCH₂CH₃ H H H H CH₂CF₃ 1235 F Cl 1 CONHCH₂CH₃ H H H H CH₂CF₃ 1236 F Cl 0 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 1237 F Cl 1 CONHCH₂CH₂CH₃ H H H H CH₂CF₃ 1238 F Cl 0 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1239 F Cl 1 CONHCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1240 F Cl 0 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1241 F Cl 1 CONHCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1242 F Cl 0 OH H H H H CH₂CF₃ 1243 F Cl 1 OH H H H H CH₂CF₃ 1244 F Cl 0 OCH₃ H H H H CH₂CF₃ 1245 F Cl 1 OCH₃ H H H H CH₂CF₃ 1246 F Cl 0 OCH₂CH₃ H H H H CH₂CF₃ 1247 F Cl 1 OCH₂CH₃ H H H H CH₂CF₃ 1248 F Cl 0 OCH₂CH₂CH₃ H H H H CH₂CF₃ 1249 F Cl 1 OCH₂CH₂CH₃ H H H H CH₂CF₃ 1250 F Cl 0 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1251 F Cl 1 OCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1252 F Cl 0 SH H H H H CH₂CF₃ 1253 F Cl 1 SH H H H H CH₂CF₃ 1254 F Cl 0 SCH₃ H H H H CH₂CF₃ 1255 F Cl 1 SCH₃ H H H H CH₂CF₃ 1256 F Cl 0 SCH₂CH₃ H H H H CH₂CF₃ 1257 F Cl 1 SCH₂CH₃ H H H H CH₂CF₃ 1258 F Cl 0 SCH₂CH₂CH₃ H H H H CH₂CF₃ 1259 F Cl 1 SCH₂CH₂CH₃ H H H H CH₂CF₃ 1260 F Cl 0 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1261 F Cl 1 SCH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1262 F Cl 0 SCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1263 F Cl 1 SCH₂CH₂CH₂CH₂CH₃ H H H H CH₂CF₃ 1264 F Cl 0 SCH₂CF₃ H H H H CH₂CF₃ 1265 F Cl 1 SCH₂CF₃ H H H H CH₂CF₃ 1266 F Cl 0 SCH₂CH₂Cl H H H H CH₂CF₃ 1267 F Cl 1 SCH₂CH₂Cl H H H H CH₂CF₃ 1268 F Cl 0 SCH₂CH₂F H H H H CH₂CF₃ 1269 F Cl 1 SCH₂CH₂F H H H H CH₂CF₃ 1270 F Cl 0 SCH₂CHF₂ H H H H CH₂CF₃ 1271 F Cl 1 SCH₂CHF₂ H H H H CH₂CF₃ 1272 F Cl 0 S(O)CH₂CH₃ H H H H CH₂CF₃ 1273 F Cl 1 S(O)CH₂CH₃ H H H H CH₂CF₃ 1274 F Cl 0 S(O)CH₂CF₃ H H H H CH₂CF₃ 1275 F Cl 1 S(O)CH₂CF₃ H H H H CH₂CF₃ 1276 F Cl 0 S(O)CH₂CH₂Cl H H H H CH₂CF₃ 1277 F Cl 1 S(O)CH₂CH₂Cl H H H H CH₂CF₃ 1278 F Cl 0 S(O)CH₂CH₂F H H H H CH₂CF₃ 1279 F Cl 1 S(O)CH₂CH₂F H H H H CH₂CF₃ 1280 F Cl 0 S(O)CH₂CHF₂ H H H H CH₂CF₃ 1281 F Cl 1 S(O)CH₂CHF₂ H H H H CH₂CF₃ 1282 F Cl 0 SCH₂CF₃ H F H H CH₂CF₃ 1283 F Cl 1 SCH₂CF₃ H F H H CH₂CF₃ 1284 F Cl 0 SCH₂CH₂Cl H F H H CH₂CF₃ 1285 F Cl 1 SCH₂CH₂Cl H F H H CH₂CF₃ 1286 F Cl 0 SCH₂CH₂F H F H H CH₂CF₃ 1287 F Cl 1 SCH₂CH₂F H F H H CH₂CF₃ 1288 F Cl 0 SCH₂CHF₂ H F H H CH₂CF₃ 1289 F Cl 1 SCH₂CHF₂ H F H H CH₂CF₃ 1290 F Cl 0 S(O)CH₂CH₃ H F H H CH₂CF₃ 1291 F Cl 1 S(O)CH₂CH₃ H F H H CH₂CF₃ 1292 F Cl 0 S(O)CH₂CF₃ H F H H CH₂CF₃ 1293 F Cl 1 S(O)CH₂CF₃ H F H H CH₂CF₃ 1294 F Cl 0 S(O)CH₂CH₂Cl H F H H CH₂CF₃ 1295 F Cl 1 S(O)CH₂CH₂Cl H F H H CH₂CF₃ 1296 F Cl 0 S(O)CH₂CH₂F H F H H CH₂CF₃ 1297 F Cl 1 S(O)CH₂CH₂F H F H H CH₂CF₃ 1298 F Cl 0 S(O)CH₂CHF₂ H F H H CH₂CF₃ 1299 F Cl 1 S(O)CH₂CHF₂ H F H H CH₂CF₃ 1300 F Me 0 SCH₂CF₃ H H H H CH₂CF₃ 1301 F Me 1 SCH₂CF₃ H H H H CH₂CF₃ 1302 F Me 0 SCH₂CH₂Cl H H H H CH₂CF₃ 1303 F Me 1 SCH₂CH₂Cl H H H H CH₂CF₃ 1304 F Me 0 SCH₂CH₂F H H H H CH₂CF₃ 1305 F Me 1 SCH₂CH₂F H H H H CH₂CF₃ 1306 F Me 0 SCH₂CHF₂ H H H H CH₂CF₃ 1307 F Me 1 SCH₂CHF₂ H H H H CH₂CF₃ 1308 F Me 0 S(O)CH₂CH₃ H H H H CH₂CF₃ 1309 F Me 1 S(O)CH₂CH₃ H H H H CH₂CF₃ 1310 F Me 0 S(O)CH₂CF₃ H H H H CH₂CF₃ 1311 F Me 1 S(O)CH₂CF3 H H H H CH₂CF₃ 1312 F Me 0 S(O)CH₂CH₂Cl H H H H CH₂CF₃ 1313 F Me 1 S(O)CH₂CH₂Cl H H H H CH₂CF₃ 1314 F Me 0 S(O)CH₂CH₂F H H H H CH₂CF₃ 1315 F Me 1 S(O)CH₂CH₂F H H H H CH₂CF₃ 1316 F Me 0 S(O)CH₂CHF₂ H H H H CH₂CF₃ 1317 F Me 1 S(O)CH₂CHF₂ H H H H CH₂CF₃ 1318 F Me 0 SCH₂CF₃ H F H H CH₂CF₃ 1319 F Me 1 SCH₂CF₃ H F H H CH₂CF₃ 1320 F Me 0 SCH₂CH₂Cl H F H H CH₂CF₃ 1321 F Me 1 SCH₂CH₂Cl H F H H CH₂CF₃ 1322 F Me 0 SCH₂CH₂F H F H H CH₂CF₃ 1323 F Me 1 SCH₂CH₂F H F H H CH₂CF₃ 1324 F Me 0 SCH₂CHF₂ H F H H CH₂CF₃ 1325 F Me 1 SCH₂CHF₂ H F H H CH₂CF₃ 1326 F Me 0 S(O)CH₂CH₃ H F H H CH₂CF₃ 1327 F Me 1 S(O)CH₂CH₃ H F H H CH₂CF₃ 1328 F Me 0 S(O)CH₂CF₃ H F H H CH₂CF₃ 1329 F Me 1 S(O)CH₂CF₃ H F H H CH₂CF₃ 1330 F Me 0 S(O)CH₂CH₂Cl H F H H CH₂CF₃ 1331 F Me 1 S(O)CH₂CH₂Cl H F H H CH₂CF₃ 1332 F Me 0 S(O)CH₂CH₂F H F H H CH₂CF₃ 1333 F Me 1 S(O)CH₂CH₂F H F H H CH₂CF₃ 1334 F Me 0 S(O)CH₂CHF₂ H F H H CH₂CF₃ 1335 F Me 1 S(O)CH₂CHF₂ H F H H CH₂CF₃

The disclosure also provides a method for preparing the aryl sulfide, the method having the following synthesis route:

R₁, R₂, R₃, R₄, R₅, R₆, X, Y, n have the same definitions as mentioned above.

Specifically, the method comprises:

heating a mixture of a nitro compound II and chlorosulfonic acid to yield a sulfonyl chloride compound III; reducing the sulfonyl chloride compound III to yield a disulfide compound IV; reducing the disulfide compound IV with hydrogen or a metal to yield an amino compound V; contacting the amino compound V with an electrophilic reagent under alkaline conditions to yield an intermediate VI; contacting the intermediate VI with substituted benzyl bromide to yield a first compound I-A; and contacting the first compound I-A with m-chloroperoxybenzoic acid or hydrogen peroxide for oxidation reaction to yield a second compound I-B.

In a class of this embodiment, the intermediate VI is synthesized as follows:

R₆, X, and Y have the same definitions as mentioned above.

Specifically, the synthesis of the intermediate VI comprises:

contacting an amino compound VII with acyl chloride or anhydride to yield an amino protected amide compound VIII; contacting the amino protected amide compound VIII with chlorosulfonic acid and heating to yield a compound IX; reducing the compound IX to yield a thiophenol compound X which is hydrolyzed under alkaline conditions and contacts with an electrophilic reagent for substitution reaction to yield the intermediate VI.

In a class of this embodiment, the compound XI is synthesized as follows:

X and Y have the same definitions as mentioned above.

Specifically, the synthesis of the compound XI comprises: reducing the compound III to yield a thiophenol compound XII, and reducing the thiophenol compound XII to yield the compound XI.

The disclosure further provides a method for preparing the aryl sulfide, the method having the following synthesis route:

R₁, R₂, R₃, R₄, R₅, R₆, X, Y, and n have the same definitions as mentioned above.

Specifically, the method comprises:

preparing a benzylamine intermediate XIII from an intermediate VII; contacting the benzylamine intermediate XIII with sulfonyl chloride, followed by reduction reaction and substitution reaction, to yield a first compound I-A; and contacting the first compound I-A with m-chloroperoxybenzoic acid or hydrogen peroxide for oxidation reaction to yield a second compound I-B.

The agriculturally acceptable salt is a derivative of the compound represented by the formula I of the disclosure. Specifically, when a hydroxyl, carboxyl, or amino exists in the structure of the formula I, the hydroxyl, carboxyl, or amino reacts with a metal or organic base to form the salt, or reacts with an inorganic acid or organic acid to yield the salt, such as potassium salt, sodium salt, magnesium salt, or calcium salt. The organic bases can be triethylamine or diisopropylamine; the inorganic acid can be hydrochloric acid, sulfuric acid, hydrobromic acid, etc.; the organic acid can be formic acid, acetic acid, methanesulfonic acid, fumaric acid, maleic acid, etc.

The compound represented by general formula I (comprising I-A and I-B) of the disclosure has unexpected high acaricidal activity. Therefore, the technical scheme of the disclosure further includes the use of the compound represented by general formula I in the preparation of acaricide drugs in agriculture or other fields. In particular, the compound of general formula I has high activity to the following species (the objects listed below are only used to illustrate but not to limit the disclosure): Tetranychidae (Tetranychus cinnabarinus, Panonychus citri, Tetranychus urticae, Panonychus ulmi, Tetranychus kanzawai, Tetranychus viennensis), Acaridae, zodiaceae, Tetranychidae, Myzus persicae, nematodes, etc.

The abovementioned compounds have good properties and thus can be used to protect the crops and livestock in agriculture and horticulture from being damaged by mites.

To obtain the ideal effect, the dosage of the compound varies with various factors, such as the compound used, the to be protected crop, the type of pest, the degree of infection, the application method, the application environment, the dosage form, etc.

8 g to 3 kg of the compound per hectare can provide adequate control of mites.

The composition of the disclosure can be applied in the form of a preparation. The compound of the general formula I is dissolved or dispersed in a carrier as an active ingredient, or configured as a preparation, so that it is easier to disperse when used as acaricide. For example, the active substances can be made into wettable powder, water dispersible granule, suspension agent, water emulsion, water agent or emulsifiable concentrate. At least one liquid or solid carrier is added to the composition, and an appropriate surfactant can be added when necessary.

The disclosure provides a method for preventing mites: applying the composition of the disclosure to the mite or a growth medium thereof. In general, the suitable effective dose is 8 g to 1000 g/ha, and an optimal effective dose is 15 g to 300 g/ha.

For some applications, for example, in agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers can be added to the acaricidal composition of the disclosure, thereby producing additional advantages and effects.

Understandably, various transformations and modifications can be made within the scope of the claims of the disclosure.

The following advantages are associated with the aryl sulfide comprising benzylamine of the disclosure:

1. The aryl sulfide comprising benzylamine exhibits excellent killing effects on various pests, especially on Tetranychus urticae, Tetranychus kanzawai and Tetranychus Panonychus

2. The compound exhibits good properties in protecting crops of agriculture and horticulture and livestock.

DETAILED DESCRIPTION

To further illustrate the disclosure, embodiments detailing an aryl sulfide comprising benzylamine and preparation method thereof are described below. It should be noted that the following embodiments are intended to describe and not to limit the disclosure.

Example 1 Preparation of N-(4-chloro-3-fluorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 249) S1. Preparation of 4-fluoro-2-methyl-5-nitrobenzenesulfonyl chloride

At room temperature, chlorosulfonic acid (34.95 g, 30 mmol) was added into a 250 mL round bottom flask, and 2-fluoro-4-methylnitrobenzene (15.5 g, 10 mmol) was slowly added into the flask in four batches. The reaction solution was exothermic obviously. Thereafter, the reaction flask was heated at 60° C., and 2 hours later, the reaction was detected to be basically completed. The reaction solution was added into 500 mL of ice-water mixture, and 400 mL of dichloromethane was added for extraction and liquid separation. 300 mL of water was added to the organic phase. After extraction and separation, the organic phase was evaporated in a rotary evaporator and extracted by silica gel column chromatography, to obtain 16.5 g of a light yellow solid (yield of 64.45%).

S2. Preparation of 1,2-bis (4-fluoro-2-methyl-5-nitrophenyl) disulfide

Under the protection of nitrogen, 4-fluoro-2-methyl-5-nitrobenzenesulfonyl chloride (12.7 g, 5 mmol) was dissolved in 200 mL of acetic acid. 40 mL concentrated hydrochloric acid was added, and the reaction solution was heated to reflux. An iron powder (11.2 g, 20 mmol) was slowly added into the reaction solution in 4 batches within 1 hour. 1.5 hours later, 20 mL of concentrated salt acid was added and stirred for an hour. Thereafter, most acetic acid in the reaction solution was evaporated, and 300 mL of ethyl acetate and 300 mL of water were added to the reaction solution for extraction and liquid separation. 150 mL of ethyl acetate was added to the water layer for extraction and liquid separation again. The organic layers were combined and washed with 50 mL of saturated sodium chloride solution, dried over 10 g of anhydrous sodium sulfate for 10 min, evaporated in a rotary evaporator, and purified by silica gel column chromatography, to obtain 7.4 g of a light brown solid (yield of 79.56%).

S3. Preparation of 5,5′-disulfide (2-fluoro-4-methylaniline)

Method 1:

1,2-bis (4-fluoro-2-methyl-5-nitrophenyl) disulfide (3.72 g, 1 mmol) was added to 30 mL of 20% hydrochloric acid. The reaction solution was heated at 60° C., and zinc powder (1.30 g, 2 mmol) was slowly added in batches and stirred for 1 hour under heating. Most of acetic acid was removed by vacuum rotary evaporation, and 100 mL of saturated sodium carbonate solution and 100 mL ethyl acetate were added to the residue for extraction and separation. The organic layer was dried over 5 g of anhydrous sodium sulfate, evaporated in a rotary evaporator, and purified by silica gel column chromatography, to yield 2.45 g of an off-white solid (yield of 78.52%).

Method 2:

1,2-bis (4-fluoro-2-methyl-5-nitrophenyl) disulfide (1.86 g, 0.5 mmol) was dissolved in 30 mL of anhydrous ethanol. The air in the reaction flask was replaced with nitrogen, and 0.3 g of palladium carbon (containing 50% water) with 10% palladium was added. The gas in the reaction flask was replaced with hydrogen, and the reaction solution was stirred in 20 atmospheric pressure in the hydrogen atmosphere at 65° C. for 10 hours. After the reaction, the palladium carbon was removed by vacuum filtration, and the reaction solution was evaporated in a rotary evaporator to obtain 1.50 g of a light brown solid (yield of 96.2%).

S4. Preparation of 2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline

Method 1:

5,5′-disulfide (2-fluoro-4-methylaniline) (1.56 g, 5 mmol) was dissolved in 30 mL of N, N-dimethylformamide (DMF). 50 mL of sodium dihydrogen phosphate (5.0 g, 41.7 mmol) aqueous solution was added to the reaction solution. The air in the reaction flash was purged by nitrogen, and sodium hydrosulfite (2.5 g, 14.4 mmol) was added. The reaction flask was heated at 60° C. for 2 hours, and then 2,2-trifluoroethyltrifluoromethane sulfonate (3.48 g, 14.4 mmol) was added and stirred for 1 hour. Thereafter, the reaction solution was added into 300 mL of water, and 200 mL of ethyl acetate was added for extraction and liquid separation. The organic layer was washed with water four times, 300 mL of water each time. After washing, the organic layer was evaporated in a rotary evaporator, and purified by silica gel column chromatography, to yield to obtain 1.68 g of light brown liquid (yield 70.29%).

¹H-NMR (400 MHz, d6-DMSO): δ=7.01 (m, 2H, Ar—H), 5.12 (s, 2H, N—H), 3.76 (dd, J=21.2, 10.4 Hz, 2H, CH₂), 2.30 (s, 3H, CH₃).

Method 2:

5,5′-disulfide (2-fluoro-4-methylaniline) (1.56 g, 5 mmol) was dissolved in 30 mL of N, N-dimethylformamide (DMF). Sodium carbonate (0.53 g, 5 mmol) and sodium hydroxymethylsulfinate (0.67 g, 5 mmol) were added, and then 2,2,2-trifluoroioethane (3.15 g, 15 mmol) was added and stirred for 1 hour. Thereafter, the reaction solution was added into 300 mL of water, and 200 mL of ethyl acetate was added for extraction and liquid separation. The organic layer was washed with water four times, 300 mL of water each time. After washing, the organic layer was evaporated in a rotary evaporator, and purified by silica gel column chromatography, to yield to obtain 1.77 g of light brown liquid (yield of 74.06%).

¹H-NMR (400 MHz, d6-DMSO): δ=7.01 (m, 2H, Ar—H), 5.12 (s, 2H, N—H), 3.76 (dd, J=21.2, 10.4 Hz, 2H, CH₂), 2.30 (s, 3H, CH₃).

S5. Preparation of N-(4-chloro-3-fluorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 249)

2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (239 mg, 1 mmol) was added to DMF (5 mL), and then potassium carbonate (138 mg, 1 mmol) and 4-bromomethyl-1-chloro-2-fluorobenzene (223 mg, 1 mmol) were added sequentially. The reaction solution was stirred at room temperature for 5 hours, added into 100 mL of water, and extracted twice with 100 mL of ethyl acetate. The organic phase was washed with water, dried over anhydrous sodium sulfate, vacuum concentrated, and purified with column chromatography to yield 252 mg of a colorless viscous liquid. The yield was 66.0%.

¹H-NMR (500 MHz, CDCl₃): δ=7.21-7.34 (m, 2H), 7.00-7.04 (m, 1H), 6.79-6.88 (m, 2H), 4.44 (d, J=8.0 Hz, 2H), 3.17 (q, J=7.5 Hz, 2H), 2.36 (d, J=21.5 Hz, 3H).

MS (m/z, ESI): 382.04 (m+H).

Example 2 Preparation of 2-fluoro-N-(3-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (compound 229) S1. Preparation of 4-fluoro-2-methyl-5-nitrophenylthiophenol

4-fluoro-2-methyl-5-nitrobenzenesulfonyl chloride (0.15 mol, 38.0 g) was placed in a 250 mL single mouthed flask, and 80 mL of hydroiodate was added. The reaction solution turned black, and was stirred at room temperature for 1 hour. Thereafter, 80 mL of saturated sodium sulfite solution was slowly added, and a yellow powdery solid appeared in the reaction solution. The yellow powdery solid was vacuum filtered and washed with water, to yield 28.0 g of a light yellow powder with a yield of 100%.

S2. Preparation of 4-fluoro-2-methyl-5-aminothiophenol

4-fluoro-2-methyl-5-nitrobenzene thiophenol (0.15 mol, 28.0 g) was dissolved in anhydrous ethanol (280 mL), and 10% palladium carbon (1.0 g, 50% water content) was added. The gas in the reaction flask was replaced by hydrogen three times, and the reaction solution was stirred overnight at room temperature under normal pressure in the hydrogen atmosphere. The reaction solution was filtered under reduced pressure to remove palladium carbon, and concentrated to dryness under reduced pressure to remove ethanol. 23.2 g of a gray white solid was obtained with a yield of 98.7%. 1H-NMR (400 MHz, d6-DMSO): δ=6.93 (m, 2H, Ar—H), 5.12 (s, 2H, N—H), 3.35 (br, 0.5H, S—H), 2.15 (s, 3H, CH3).

S3. Preparation of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl) thio) aniline

4-fluoro-2-methyl-5-aminothiophenol (25 mmol, 3.9 g) was dissolved in anhydrous DMF (50 mL), and then sodium carbonate (50 mmol, 5.3 g, 2 eq) and sodium hydroxymethyl sulfite (25 mmol, 3.4 g, 1 eq) were added successively. Thereafter, trifluoroethane (27.5 mmol, 5.8 G, 1.1 eq) was added under ice bath. The reaction solution was stirred at room temperature for 2 hours until the reaction was complete. The reaction solution was poured into water, and extracted and separated with ethyl acetate. The organic layer was washed with water for three times, and then washed with saturated salt water once. After separation, the organic layer was dried over anhydrous sodium sulfate, and dried under reduced pressure to yield a light brown oily liquid. The light brown oily liquid was purified by column chromatography with a mobile phase of petroleum ether:ethyl acetate=10:1, to yield 4.2 g of a yellow oily product with a yield of 71.2%.

1H-NMR (400 MHz, d6-DMSO): δ=7.01 (m, 2H, Ar—H), 5.12 (s, 2H, N—H), 3.76 (dd, J=21.2, 10.4 Hz, 2H, CH2), 2.30 (s, 3H, CH3).

S4. Preparation of 2-fluoro-N-(3-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 229)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.28-7.33 (m, 1H), 7.05-7.14 (m, 2H), 6.94-6.99 (m, 1H), 6.85 (d, J=15.0 Hz, 1H), 6.75 (d, J=10.5 Hz, 1H), 4.36 (d, J=7.0 Hz, 2H), 3.17 (q, J=12.0 Hz, 2H), 2.35 (d, J=6.0 Hz, 3H).

MS (m/z, ESI): 388.07 (m+H).

Example 3 Preparation of 2-fluoro-N-(3-methoxybenzyl)-4-methyl-5-(2,2,2-trifluoroethyl) thio) aniline (Compound 239) S1: Preparation of N-(2-fluoro-4-methylphenyl) acetamide

2-fluoro-4-methylaniline (125 g, 1 mol) was dissolved in dichloromethane (1 L), and triethylamine (111 g, 1.1 mol) was added. The mixture solution was cooled in an ice salt bath until the internal temperature thereof was 0° C. Acetic anhydride (102 g, 1 mol) was added slowly. Thereafter, the reaction solution was stirred for reaction at room temperature for 3 hours. 2 L of water was added to the reaction solution for extraction and separation. The organic phase was dried over anhydrous sodium sulfate, and evaporated in a rotary evaporator, to yield 162 g of a white solid, with a yield of 97.0%.

S2: Preparation of 5-acetamino-4-fluoro-2-methylbenzenesulfonyl chloride

N-(2-fluoro-4-methylphenyl) acetamide (145 g, 868 mmol) was added to a 1 L round bottom flask, and a tail gas absorption device was disposed on the round bottom flask. Chlorosulfonic acid (302 g, 2.60 mol) was slowly added and electrically stirred. Thereafter, the mixed solution was heated until the internal temperature thereof was 60° C. 3 hours later, the temperature was reduced to room temperature. The reaction liquid was stirred and slowly added to 2 kg of ice, and extracted twice with 500 mL of ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and evaporated in a rotary evaporator, to yield 175.2 g of an off-white solid, with a yield of 76.2%.

S3: Preparation of N-(2-fluoro-5-mercapto-4-methylphenyl) acetamide

5-acetamino-4-fluoro-2-methylbenzenesulfonyl chloride (174.6 g, 660 mmol) was added to acetic acid (700 mL), and red phosphorus (50 g, 1.61 mol) and iodine (2 g) were added sequentially. The reaction liquid was heated to a reflux state and stirred for 3 hours. The reaction liquid was concentrated under reduced pressure to remove acetic acid. 1.5 L of water and 1 L of ethyl acetate were added for extraction and liquid separation. 500 mL of ethyl acetate was added to the aqueous phase to separate the liquid. The organic phases were combined, washed with sodium carbonate solution, separated and evaporated in a rotary evaporator to yield 103.4 g of a light brown solid with a yield of 78.4%.

S4: Preparation of 5-amino-4-fluoro-2-methylthiophenol

N-(2-fluoro-5-mercapto-4-methylphenyl) acetamide (101 g, 507 mmol) was added to 10% sodium hydroxide aqueous solution (1 L), heated and refluxed for 5 hours. The pH of the reaction solution was adjusted to 7 with dilute hydrochloric acid, and then the reaction solution was extracted with ethyl acetate. The organic phase was dried with anhydrous sodium sulfate and concentrated under reduced pressure. 62.7 g of an off-white solid was obtained with a yield of 78.8%.

S5: Preparation of 2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline

5-amino-4-fluoro-2-methylthiophene (15.72 g, 0.1 mol) was dissolved in DMF (100 mL), and then potassium hydroxide (5.6 g, 0.1 mol), sodium formaldehyde bisulfite (15.4 g, 0.1 mol) and trifluoro iodoethane (20.9 g, 0.1 mol) were successively added. The reaction solution was stirred at room temperature for 5 hours, and then added into 500 mL of water. 500 mL of ethyl acetate extract was added for extraction and liquid separation. 200 mL of ethyl acetate was added to the aqueous phase to extract and separate the liquid. The organic layers were combined, washed with 500 mL of water twice. The organic phase was separated, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by column chromatography. 16.6 g of a light brown liquid was obtained with a yield of 69.45%.

S6: Preparation of 2-fluoro-N-(3-methoxybenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 239)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.24-7.28 (m, 1H), 6.76-6.98 (m, 5H), 4.30 (d, J=16.5 Hz, 2H), 3.75 (s, 3H), 3.15 (q, J=12.0 Hz, 2H), 2.35 (s, 3H).

MS (m/z, ESI): 360.09 (m+H).

Example 4 Preparation of 2-fluoro-4-methyl-n-(3-nitrobenzyl)-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 241)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=8.10 (d, J=10.0 Hz, 1H), 7.58-7.60 (m, 2H), 7.44-7.47 (m, 1H), 6.87 (d, J=14.5 Hz, 1H), 6.68 (d, J=11.0 Hz, 1H), 4.75 (d, J=8.0 Hz, 2H), 3.15 (q, J=12.0 Hz, 2H), 2.35 (s, 3H).

MS (m/z, ESI): 375.06 (m+H).

Example 5 Preparation of N-(3,4-dichlorobenzyl)-2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl) thio) aniline (Compound 247)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.34-7.45 (m, 2H), 7.19 (dd, J₁=3.0 Hz, J₂=10.5 Hz, 1H), 6.73 (d, J=10.5 Hz, 1H), 6.55 (d, J=10.5 Hz, 1H), 4.31 (d, J=6.5 Hz, 2H), 3.17 (q, J=12.5 Hz, 2H), 2.36 (d, J=14.0 Hz, 3H).

MS (m/z, ESI): 398.01 (m+H).

Example 6 Preparation of 2-(((2-fluoro-4-methyl-5-((2,2, 2-trifluoroethyl) thio) phenyl) amino) methyl) benzoate (Compound 53)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.98 (d, J=9.5 Hz, 1H), 7.46-7.48 (m, 2H), 7.31-7.34 (m, 1H), 6.80-6.84 (m, 2H), 4.68 (s, 2H), 3.92 (s, 3H), 3.18 (q, J=12.0 Hz, 3H), 2.32 (s, 3H).

MS (m/z, ESI): 388.06 (m+H).

Example 7 Preparation of N-(3-bromobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 233)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.51 (s, 1H), 7.38-7.42 (m, 1H), 7.23-7.40 (m, 2H), 6.85-6.88 (m, 1H), 6.76 (d, J=11.0 Hz, 1H), 4.34 (s, 2H), 3.17 (q, J=12.0 Hz, 2H), 2.36 (d, J=10.0 Hz, 3H).

MS (m/z, ESI): 408.00 (m+H).

Example 8 Preparation of 2-fluoro-N-(4-iodobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 707)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.72 (s, 1H), 7.62 (d, J=9.5 Hz, 1H), 7.29-7.32 (m, 1H), 7.08-7.12 (m, 1H), 6.87 (d, J=15.5 Hz, 1H), 6.76 (d, J=11.0 Hz, 1H), 4.32 (s, 2H), 3.17 (q, J=12.0 Hz, 2H), 2.33 (d, J=21.5 Hz, 3H).

MS (m/z, ESI): 455.87 (m+H).

Example 9 Preparation of N-(3-bromo-5-fluorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 251)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.19-7.27 (m, 3H) 6.78-6.87 (m, 2H), 4.37 (d, J=7.0 Hz, 2H), 3.21 (q, J=12.0 Hz, 2H), 2.34-2.36 (m, 3H).

MS (m/z, ESI): 325.98 (m+H).

Example 10 Preparation of 2-fluoro-n-(4-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 709)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl₃): δ=7.30-7.34 (m, 2H), 6.96-7.06 (m, 2H), 6.82 (d, J=11.5 Hz, 1H), 6.76 (d, J=11.0 Hz, 1H), 4.31 (d, J=7.0 Hz, 2H), 3.22 (q, J=12.5 Hz, 2H), 2.34-2.36 (m, 3H).

MS (m/z, ESI): 348.07 (m+H).

Example 11 Preparation of N-(4-chlorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 711)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.35 (s, 1H), 7.22-7.28 (m, 3H), 6.87 (d, J=15.0 Hz, 1H), 6.76 (d, J=11.0 Hz, 1H), 4.31 (d, J=7.0 Hz, 2H), 3.21 (q, J=12.0 Hz, 2H), 2.34-2.37 (m, 3H).

MS (m/z, ESI): 364.05 (m+H).

Example 12 Preparation of N-benzyl-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 1105)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.18-7.28 (m, 6H), 6.73-6.82 (m, 2H), 4.26 (s, 2H), 3.06-3.16 (m, 2H), 2.27 (s, 3H).

MS (m/z, ESI): 330.09 (m+H).

Example 13 Preparation of 4-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) phenyl) amino) methyl) benzylnitrile (Compound 721)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.64 (d, J=10.0 Hz, 2H), 7.46 (d, J=10.5 Hz, 2H), 6.88 (d, J=18.5 Hz, 1H), 6.66 (d, J=11.0 Hz, 1H), 4.44 (s, 2H), 3.14 (q, J=7.0 Hz, 2H), 2.36 (s, 3H).

MS (m/z, ESI): 355.08 (m+H).

Example 14 Preparation of methyl 4-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) phenyl) amino) methyl benzoate (Compound 739)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.94 (d, J=10.5 Hz, 2H), 7.34 (d, J=10.0 Hz, 2H), 6.77 (d, J=15.5 Hz, 1H), 6.68 (d, J=10.5 Hz, 1H), 4.34 (s, 2H), 3.83 (s, 3H), 3.07 (q, J=12.0 Hz, 2H), 2.27 (s, 3H).

MS (m/z, ESI): 388.06 (m+H).

Example 15 Preparation of 2-fluoro-N-(4-methoxybenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 1131)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.20-7.26 (m, 2H), 7.67-7.84 (m, 4H), 5.07 (s, 1H), 4.20 (s, 2H), 3.69 (s, 3H), 3.13 (q, J=12.0 Hz, 2H), 2.28 (s, 3H).

MS (m/z, ESI): 360.09 (m+H).

Example 16 Preparation of 2-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio) phenyl) amino) methyl) benzylnitrile (Compound 33)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.68 (d, J=9.5 Hz, 1H), 7.50-7.55 (m, 2H), 7.35-7.37 (m, 1H), 6.85 (d, J=8.5 Hz, 1H), 6.74 (d, J=10.5 Hz, 1H), 3.18 (q, J=12.0 Hz, 2H), 2.35 (s, 3H).

MS (m/z, ESI): 355.08 (m+H).

Example 17 Preparation of 2-fluoro-4-methyl-N-(4-nitrobenzyl)-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 755)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.68 (d, J=9.5 Hz, 1H), 7.50-7.55 (m, 2H), 7.35-7.37 (m, 1H), 6.85 (d, J=8.5 Hz, 1H), 6.74 (d, J=10.5 Hz, 1H), 4.49 (s, 2H), 3.18 (q, J=12.0 Hz, 2H), 2.35 (s, 3H).

MS (m/z, ESI): 375.06 (m+H).

Example 18 Preparation of 2-fluoro-N-(2-iodobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (Compound 31)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.86 (d, J=10.0 Hz, 1H), 7.30-7.33 (m, 2H), 6.95-7.00 (m, 1H), 6.85 (d, J=8.5 Hz, 1H), 6.73 (d, J=11.0 Hz, 1H), 4.34 (s, 2H), 3.20 (q, J=12.0 Hz, 2H), 2.35 (s, 3H).

MS (m/z, ESI): 455.87 (m+H).

Example 19 Preparation of 2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl) thio)-N-(2-(trifluoromethoxy) benzyl) aniline (Compound 1107)

The operations are the same as that in S5 of Example 1.

¹H-NMR (500 MHz, CDCl3): δ=7.30-7.53 (m, 4H), 6.85 (d, J=16.5 Hz, 1H), 6.73 (d, J=10.5 Hz, 1H), 4.44 (s, 2H), 3.17 (q, J=12.0 Hz, 2H), 2.36 (s, 3H).

MS (m/z, ESI): 413.95 (m+H).

Example 20 Preparation of 2-fluoro-n-(4-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) sulfinyl) aniline (Compound 710)

2-fluoro-N-(4-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl) thio) aniline (347 mg, 1 mmol) was dissolved in chloroform (5 mL). m-chloroperoxybenzoic acid (172 mg, 1 mmol) was added under an ice bath. The reaction solution was stirred for 1 hour, and 50 mL of ethyl acetate and 50 mL of water were added for extraction and liquid separation. 50 mL of ethyl acetate was added to the aqueous phase. The organic phases were combined, washed with 50 mL of saturated salt water, evaporated in a rotary evaporator and purified by silica gel column chromatography, to obtain 288 mg of a white solid, with a yield of 79.3%.

¹H-NMR (500 MHz, CDCl3): δ=7.30-7.34 (m, 2H), 6.96-7.06 (m, 2H), 6.85 (d, J=11.5 Hz, 1H), 6.56 (d, J=11.0 Hz, 1H), 4.31 (d, J=7.0 Hz, 2H), 3.22 (q, J=12.5 Hz, 2H), 2.26 (s, 3H).

MS (m/z, ESI): 364.07 (m+H).

Example 21 Preparation of 2-((((2-Fluoro-4-methyl-5-((2,2, 2-trifluoroethyl) sulfonyl) phenyl) amino) methyl) benzoate (Compound 54)

The operations are the same as that in S5 of Example 1 and Example 20.

1H-NMR (500 MHz, CDCl3): δ=7.94-8.04 (m, 1H), 7.45-7.48 (m, 2H), 7.25-7.28 (m, 2H), 6.82 (d, J=14.5 Hz, 1H), 4.73 (s, 2H), 3.94 (s, 3H), 3.29 (q, J=18.0 Hz, 2H), 2.23 (s, 3H).

MS (m/z, ESI): 404.1 (m+H), 424.1 (m+Na).

Example 22 Preparation of 5-Fluoro-2-((((2-Fluoro-4-methyl-5-(2,2, 2-trifluoroethyl) thio) phenyl) amino) methyl) benzoate (Compound 303)

The operations are the same as that in S5 of Example 1.

1H-NMR (500 MHz, CDCl3): δ=7.68 (dd, J₁=3.5 Hz, J₂=11.5 Hz, 1H), 7.45 (dd, J₁=7.0 Hz, J₂=10.5 Hz, 1H), 7.16 (t, J=10 Hz, 1H), 6.81 (dd, J₁=10.5 Hz, J₂=17.5 Hz, 2H), 4.65 (s, 2H), 3.92 (s, 3H), 3.19 (q, J=7.5 Hz, 2H), 2.33 (s, 3H).

MS (m/z, ESI): 406.5 (m+H).

Example 23 Preparation of 2-((((4-chloro-2-fluoro-5-((2,2, 2-trifluoroethyl) thio) phenyl) amino) methyl) benzoate (Compound 1202)

The operations are the same as that in S5 of Example 1.

1H-NMR (500 MHz, CDCl3): δ=8.00 (dd, J₁=1.5 Hz, J₂=9.5 Hz, 1H), 7.43-7.50 (m, 2H), 7.33-7.38 (m, 1H), 7.05 (d, J=14 Hz, 1H), 6.91 (d, J=6.0 Hz, 1H), 4.69 (s, 2H), 3.92 (s, 3H), 3.32 (q, J=14.0 Hz, 2H).

MS (m/z, ESI): 408.5 (m+H), 430.5 (m+Na).

Example 24 Preparation of 2-Fluoro-N-(4-Fluoro-Benzyl)-4-methyl-5-((2,2, 2-trifluoroethyl) sulfide) aniline (hydrochloride of Compound 709)

2-fluoro-N-(4-fluoro-benzyl)-4-methyl-5-((2,2, 2-trifluoroethyl) sulfide) aniline (347 mg, 1 mmol) was dissolved in methanol (5 mL), and 30% hydrogen chloride methanol solution (5 mL) was added. The mixed solution was stirred at room temperature for 1 hour, and distilled under reduced pressure to remove the solvent and hydrogen chloride. 384 mg of a white solid was obtained with a yield of 100%.

¹H-NMR (500 MHz, DMSO): δ=7.11-7.28 (m, 6H), 6.75-6.85 (m, 2H), 4.58 (d, J=7.0 Hz, 2H), 3.22 (q, J=12.5 Hz, 2H), 2.34-2.36 (m, 3H).

MS (m/z, ESI): 348.07 (m+H).

Example of Preparation 1

Emulsifiable Concentrate Comprising 8% of Compound 709

8 parts of the compound 709 were dissolved in a mixture of 10 parts of methylnaphthalene, 2 parts of methylpyrrolidone and 20 parts of methyl oleate 1169. The mixture was stirred, and 8 parts of calcium dodecyl benzene sulfonate and 4 parts of tristyrene phenol polyoxyethylene polyoxypropylene ether were added. The balance was aromatic solvent oil until the total weight was 100 parts. The mixed solution was stirred to yield an emulsifiable concentrate comprising 8% of the compound 709.

Example of Preparation 2

Suspension Agent Comprising 20% of Compound 710

20 parts of the compound 71, 1 part of magnesium aluminum silicate and 0.3 parts of benzoic acid were mixed for use. 3 parts of ammonium tristyrylphenol polyoxyethylene ether sulfate, 3 parts of a block polyether, 5 parts of ethylene glycol and water were sheared and mixed in a high-speed shear machine. Then, the sheared additives were added to the solid mixture, stirred and sheared, and then ground in a grinder for 3 hours. Thereafter, the glass beads were filtered out to obtain a suspending agent comprising 20% of the compound 710.

Example of Preparation 3

Wettable Powders Comprising 20% of Compound 53

20 parts of the compound 53 was added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignosulfonate, 20 parts of silica hydrate and 54 parts of clay. The mixture was fully stirred to yield wettable powders comprising 20% of the compound 53.

Example of Preparation 4

Granules Comprising 5% of Compound 53

2 parts of sodium dodecylbenzene sulfonate, 10 parts of bentonite and 83 parts of clay were added to 5 parts of the compound 53. The mixture was stirred fully, and appropriate amount of water was added. The mixture was continuously stirred, granulated with a granulator, and air dried to yield granules comprising 5% of the compound 53.

Example of Preparation 5

Dry Flowable Comprising 30% of Compound 53

30 parts of the compound 53, 20 parts of sodium lignosulfonate, 2 parts of a wetting agent, and 2 parts of white carbon black were mixed, and Kaolin was added until the total weight was 100 parts. The mixture was mixed with water, smashed and homogenized with a shearing machine, ground in a sand mill, and spray dried to yield a dry flowable comprising 30% of the compound 53.

Example of Use

Activity Test of Tetranychus cinnabarinus

The compound under test was dissolved in acetone and diluted to desired concentration with 0.1% Tween 80 solution with acetone content not exceeding 5%.

One true leaf was removed from the bean seedlings having two true leaves. Tanyanychus cinarinus was inoculated and the cardinal number thereof investigated. The whole plant was sprayed with a handheld sprayer, and each treatment was repeated for 3 times. After treatment, the bean seedlings were cultured in a constant temperature room. 72 hours later, the number of live mites was investigated and the mortality rate was calculated. The number of Tetranychus cinnabarinus was 100-200 per inoculation.

Mortality=(number of inoculated mites−number of live mites after treatment)×number of inoculated mites×100%.

In this test, the following compounds showed a lethal rate of over 90% against mites at 100 ppm (100 mg/L): Nos 1, 2, 3, 4, 5, 6, 25, 26, 27, 28, 29, 30, 33, 34, 39, 40, 41, 42, 43, 44, 53, 54, 55, 56, 57, 58, 67, 68, 71, 72, 95, 96, 97, 98, 99, 100, 108, 109, 110, 111, 139, 140, 141, 142, 153, 154, 155, 156, 167, 168, 169, 170, 229, 230, 231, 232, 247, 248, 249, 250, 253, 254, 255, 256, 257, 258, 275, 276, 277, 278, 283, 284, 285, 286, 289, 290, 291, 292, 293, 294, 303, 304, 305, 306, 307, 308, 317, 318, 321, 322, 331, 332, 355, 356, 357, 358, 366, 367, 368, 369, 423, 424, 425, 426, 507, 508, 509, 510, 523, 524, 535, 536, 537, 538, 577, 578, 619, 620, 635, 636, 647, 648, 649, 650, 805, 806, 807, 808, 817, 818, 819, 820, 929, 930, 931, 932, 957, 958, 1029, 1030, 1031, 1032, 1043, 1044, 1045, 1046, 1071, 1072, 1113, 1114, 1115, 1116, 1117, 1118, 1125, 1126, 1165, 1166, 1167, 1168, 1177, 1178, 1202, 1203, 1204, 1205, 1216, 1217, 1256, 1257, 1264, 1265, 1266, 1267, 1268, 1269, 1270, 1271, 1274, 1275, 1282, 1283, 1284, 1285, 1286, 1287, 1288, 1289, 1292, 1293, 1300, 1301, 1302, 1303, 1304, 1305, 1306, 1307, 1310, 1311, 1318, 1319, 1320, 1321, 1322, 1323, 1324, 1325, 1328, 1329.

In this test, the following compounds showed a lethal rate of more than 90% against mites at 25 ppm (25 mg/L): Nos 53, 54, 55, 56, 108, 109, 303, 304, 305, 306, 366, 367, 535, 536, 1165, 1166, 1167, 1168, 1177, 1178, 1202, 1203, 1264, 1265, 1282, 1283, 1300, 1301, 1318, 1319.

In this test, the following compounds showed a lethal rate of more than 90% against mites at 6.25 ppm (6.25 mg/L): Nos 53, 54, 303, 304, 1165, 1166, 1202, 1203.

According to the above method, the compound Nos 53, 54, 303, 304, 1165, 1166, 1202 and 1203 of the disclosure were selected to carry out the acaricidal parallel test with bifenazate and cyflumetofen. The test results are shown in Table 2 below:

TABLE 2 Test data Compound No: Concentration (ppm) Mortality % 53 3.12 99 54 3.12 100 303 3.12 99 304 3.12 98 1165 3.12 99 1166 3.12 98 1202 3.12 97 1203 3.12 98 Bifenazate 3.12 85 Cyflumetofen 3.12 72

It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications. 

What is claimed is:
 1. An aryl sulfide comprising benzylamine, being represented by formula I, or an agriculturally acceptable salt thereof;

wherein: n is 0, 1 or 2; X and Y at each occurrence represent hydrogen, fluorine, chlorine, bromine, iodine, a cyano group, a C₁₋₄ alkyl, a C₁₋₄ haloalkyl, a C₁₋₄ alkoxy, or a C₁₋₄ haloalkoxy; R₁, R₂, R₃, R₄, and R₅ at each occurrence represent hydrogen, fluorine, chlorine, bromine, iodine, a cyano group, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, sulphydryl, C₁₋₁₀ alkyl, C₁₋₁₀ haloalkyl, C₁₋₁₀ alkoxy, haloalkoxy, alkoxycarbonyl, C₁₋₁₀ haloalkoxycarbonyl, C₁₋₁₀ alkylsulfonyloxy, alkylsulfonyl, alkylthiol, C₁₋₁₀ haloalkylthiol, C₂₋₁₀ ethoxycarbonyl, C₁₋₁₀ alkyl carbonyl, amino carbonyl, C₁₋₁₀ N-alkyl carbonyl, N, N-dimethylcarbonyl, N, N-dimethylthiocarbonyl, C₁₋₁₀ N-alkyl thiocarbonyl, 2-oxoprooxycarbonyl, or methoxymethoxycarbonyl; and R₆ represents C₁₋₆ haloalkyl, C₂₋₆ alkynyl, C₂₋₆ alkenyl, C₁₋₆ alkyl, C₃₋₆ cycloalkyl, or C₃₋₆ epoxy alkyl.
 2. The aryl sulfide of claim 1, wherein in formula I, n is 0 or 1; X is fluorine, chlorine, or methyl; Y is chlorine or methyl; R₁ is hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, hydroxymethyl, a cyano group, trifluoromethyl, C₁₋₃ alkyl, C₁₋₄ alkoxycarbonyl, acetyl, propionyl, C₁₋₃ alkoxy, ethylthio, 2-fluoroethanothioxy, 2-chloroethanothioxy, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, propylthio, 2,2,2-trifluoroethylsulfinyl, vinyloxycarbonyl, 2,2, 2-trifluoroethoxycarbonyl, or N-methylcarbonyl; R₂ is hydrogen, fluorine, or chlorine; R₃ is hydrogen, fluorine, chlorine, bromine, or a cyano group; R₄ and R₅ at each occurrence represent hydrogen; and R₆ is N-propyl or 2,2,2-trifluoroethyl.
 3. The aryl sulfide of claim 2, wherein n is 0 or 1; X is fluorine; Y is chlorine or methyl; R₁ is methoxycarbonyl, ethoxycarbonyl, ethylthio, or 2,2,2-trifluoroethylthio; R₂, R₄, and R₅ at each occurrence represent hydrogen; R₃ is hydrogen, fluorine, chlorine, or a cyano group; and R₆ is 2,2,2-trifluoroethyl.
 4. The aryl sulfide of claim 1, wherein the formula I comprises:


5. A method for preparing the aryl sulfide of claim 1, the method having the following synthesis route:

the method comprising: heating a mixture of a nitro compound II and chlorosulfonic acid to yield a sulfonyl chloride compound III; reducing the sulfonyl chloride compound III to yield a disulfide compound IV; reducing the disulfide compound IV with hydrogen or a metal to yield an amino compound V; contacting the amino compound V with an electrophilic reagent under alkaline conditions to yield an intermediate VI; contacting the intermediate VI with substituted benzyl bromide to yield a first compound I-A; and contacting the first compound I-A with m-chloroperoxybenzoic acid or hydrogen peroxide for oxidation reaction to yield a second compound I-B.
 6. A method for preparing the aryl sulfide of claim 1, the method having the following synthesis route:

the method comprising: preparing a benzylamine intermediate XIII from an intermediate VII; contacting the benzylamine intermediate XIII with sulfonyl chloride, followed by reduction reaction and substitution reaction, to yield a first compound I-A; and contacting the first compound I-A with m-chloroperoxybenzoic acid or hydrogen peroxide for oxidation reaction to yield a second compound I-B.
 7. A method of control of mites, the method comprising applying the aryl sulfide of claim 1 or a salt thereof.
 8. A method of control of nematodes, the method comprising applying the aryl sulfide of claim 1 or a salt thereof.
 9. An agricultural composition, comprising the aryl sulfide of claim 1, an agricultural salt and at least one liquid or solid carrier.
 10. A method for control of an invertebrate pest, the method comprising treating the invertebrate pest, a food chain thereof, a habitat or breeding place, or a plant and soil where the invertebrate pest grows with the aryl sulfide of claim 1 and an agricultural salt thereof.
 11. The method of claim 10, comprising treating the plant with an insecticidally effective dose of a compound represented by formula I and an agricultural salt thereof. 